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Sample records for ag-pd bimetallic nanostructures

  1. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-10-21

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag(+)/Pd(2+) is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems.

  2. Controllable galvanic synthesis of triangular Ag-Pd alloy nanoframes for efficient electrocatalytic methanol oxidation.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Yu, Sijia; Chen, Junze; Liao, Yusen; Xue, Can

    2015-06-08

    Triangular Ag-Pd alloy nanoframes were successfully synthesized through galvanic replacement by using Ag nanoprisms as sacrificial templates. The ridge thickness of the Ag-Pd alloy nanoframes could be readily tuned by adjusting the amount of the Pd source during the reaction. These obtained triangular Ag-Pd alloy nanoframes exhibit superior electrocatalytic activity for the methanol oxidation reaction as compared with the commercial Pd/C catalyst due to the alloyed Ag-Pd composition as well as the hollow-framed structures. This work would be highly impactful in the rational design of future bimetallic alloy nanostructures with high catalytic activity for fuel cell systems.

  3. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction

    NASA Astrophysics Data System (ADS)

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-09-01

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems.We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03600j

  4. Trimetallic nanostructures: the case of AgPd/Pt multiply twinned nanoparticles

    PubMed Central

    Khanal, Subarna; Bhattarai, Nabraj; Velázquez-Salazar, J. Jesús; Bahena, Daniel; Soldano, German; Ponce, Arturo; Mariscal, Marcelo M.; Mejía-Rosales, Sergio; José-Yacamán, Miguel

    2013-01-01

    We report the synthesis, structural characterization, and atomistic simulations of AgPd/Pt trimetallic (TM) nanoparticles. Two types of structure were synthesized using a relatively facile chemical method: multiply twinned core-shell, and hollow particles. The nanoparticles were small in size, with an average diameter of 11 nm and a narrow distribution, and their characterization by aberration corrected scanning transmission electron microscopy allowed us to probe the structure of the particles at atomistic level. In some nanoparticles, the formation of a hollow structure was also observed, that facilitates the alloying of Ag and Pt in the shell region and the segregation of Ag atoms in the surface, affecting the catalytic activity and stability. We also investigated the growth mechanism of the nanoparticles using grand canonical Monte Carlo simulations, and we have found that Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process. We found very good agreement between the simulated structures and those observed experimentally. PMID:24165796

  5. Global optimization of bimetallic cluster structures. II. Size-matched Ag-Pd, Ag-Au, and Pd-Pt systems.

    PubMed

    Rossi, Giulia; Ferrando, Riccardo; Rapallo, Arnaldo; Fortunelli, Alessandro; Curley, Benjamin C; Lloyd, Lesley D; Johnston, Roy L

    2005-05-15

    Genetic algorithm global optimization of Ag-Pd, Ag-Au, and Pd-Pt clusters is performed. The 34- and 38-atom clusters are optimized for all compositions. The atom-atom interactions are modeled by a semiempirical potential. All three systems are characterized by a small size mismatch and a weak tendency of the larger atoms to segregate at the surface of the smaller ones. As a result, the global minimum structures exhibit a larger mixing than in Ag-Cu and Ag-Ni clusters. Polyicosahedral structures present generally favorable energetic configurations, even though they are less favorable than in the case of the size-mismatched systems. A comparison between all the systems studied here and in the previous paper (on size-mismatched systems) is presented.

  6. Crystalline structure-dependent growth of bimetallic nanostructures.

    PubMed

    Li, Qian; Jiang, Ruibin; Ming, Tian; Fang, Caihong; Wang, Jianfang

    2012-11-21

    Morphological control of multimetallic nanostructures is crucial for obtaining shape-dependent physical and chemical properties. Up to date, control of the shapes of multimetallic nanostructures has remained largely empirical. Multimetallic nanostructures have been produced mostly through seed-mediated growth. Understanding the role played by starting nanocrystal seeds can help in controlling the shape and in turn the plasmonic and catalytic properties of multimetallic nanostructures. In this work, we have studied the effect of the crystalline structure and shape of Au nanocrystal seeds on the morphology of the resultant bimetallic nanostructures. Single-crystalline Au nanorods, multiply twinned Au nanorods, and multiply twinned Au nanobipyramids were employed as the starting seeds. Both silver and palladium exhibit highly preferential growth on the side surfaces of the single-crystalline Au nanorods, giving rise to bimetallic cuboids, whereas they prefer to grow at the ends of the multiply twinned Au nanorods and nanobipyramids, giving rise to bimetallic nanorods. These results indicate that the morphology of the bimetallic nanostructures is highly dependent on the crystalline structure of the Au nanocrystal seeds. Our results will be useful for guiding the preparation of multimetallic nanostructures with desired shapes and therefore plasmonic properties for various plasmon-based applications.

  7. Ordered macroporous bimetallic nanostructures: design, characterization, and applications.

    PubMed

    Lu, Lehui; Eychmüller, Alexander

    2008-02-01

    Ordered porous metal nanomaterials have current and future potential applications, for example, as catalysts, as photonic crystals, as sensors, as porous electrodes, as substrates for surface-enhanced Raman scattering (SERS), in separation technology, and in other emerging nanotechnologies. Methods for creating such materials are commonly characterized as "templating", a technique that involves first the creation of a sacrificial template with a specific porous structure, followed by the filling of these pores with desired metal materials and finally the removal of the starting template, leaving behind a metal replica of the original template. From the viewpoint of practical applications, ordered metal nanostructures with hierarchical porosity, namely, macropores in combination with micropores or mesopores, are of particular interest because macropores allow large guest molecules to access and an efficient mass transport through the porous structures is enabled while the micropores or mesopores enhance the selectivity and the surface area of the metal nanostructures. For this objective, colloidal crystals (or artificial opals) consisting of three-dimensional (3D) long-range ordered arrays of silica or polymer microspheres are ideal starting templates. However, with respect to the colloidal crystal templating strategies for production of ordered porous metal nanostructures, there are two challenging questions for materials scientists: (1) how to uniformly and controllably fill the interstitial space of the colloidal crystal templates and (2) how to generate ordered composite metal nanostructures with hierarchical porosity. This Account reports on recent work in the development and applications of ordered macroporous bimetallic nanostructures in our laboratories. A series of strategies have been explored to address the challenges in colloidal crystal template techniques. By rationally tailoring experimental parameters, we could readily and selectively design

  8. Ag-Pd-Si (009)

    NASA Astrophysics Data System (ADS)

    Carow-Watamura, U.; Louzguine, D. V.; Takeuchi, A.

    This document is part of Part 1 http://dx.doi.org/10.1007/97.etType="URL"/> 'Systems from Ag-Al-Ca to Au-Pd-Si' of Subvolume B 'Physical Properties of Ternary Amorphous Alloys' of Volume 37 'Phase Diagrams and Physical Properties of Nonequilibrium Alloys' of Landolt-Börnstein - Group III 'Condensed Matter'. It contains the Chapter 'Ag-Pd-Si (009)' with the content:

  9. Fabrication of bimetallic nanostructures via aerosol-assisted electroless silver deposition for catalytic CO conversion.

    PubMed

    Byeon, Jeong Hoon; Kim, Jang-Woo

    2014-03-12

    Bimetallic nanostructures were fabricated via aerosol-assisted electroless silver deposition for catalytic CO conversion. An ambient spark discharge was employed to produce nanocatalysts, and the particles were directly deposited on a polytetrafluoroethylene substrate for initiating silver deposition to form Pd-Ag, Pt-Ag, Au-Ag bimetallic nanostructures as well as a pure Ag nanostructure. Kinetics and morphological evolutions in the silver deposition with different nanocatalysts were comparatively studied. The Pt catalyst displayed the highest catalytic activity for electroless silver deposition, followed by the order Pd > Au > Ag. Another catalytic activity of the fabricated bimetallic structures in the carbon monoxide conversion was further evaluated at low-temperature conditions. The bimetallic systems showed significantly higher catalytic activity than that from a pure Ag system.

  10. Preparation of Ag/Au bimetallic nanostructures and their application in surface-enhanced fluorescence.

    PubMed

    Dong, Jun; Ye, Yanyan; Zhang, Wenhui; Ren, Zebin; Huo, Yiping; Zheng, Hairong

    2015-11-01

    An effective substrate for surface-enhanced fluorescence, which consists of cluster Ag/Au bimetallic nanostructures on a copper surface, was synthesized via a multi-stage galvanic replacement reaction of a Ag cluster in a chlorauric acid (HAuCl4) solution at room temperature. The fabricated silver/gold bimetallic cluster were found to yield large surface-enhanced fluorescence (SEF) enhancement factors for rhodamine 6G probe molecules deposited on the substrate, and also the fluorescence efficiency is critically dependent on the period of nanostructure growth. With the help of proper control reaction conditions, such as the reaction time, and concentration of reaction solutions, the maximum fluorescence enhanced effect was obtained. Therefore, the bimetallic nanostructure substrate also can be adapted to studies in SEF, which will expand the application of SEF.

  11. An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

    DOE PAGES

    Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; ...

    2015-09-11

    Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic properties and thermalmore » stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.« less

  12. An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

    SciTech Connect

    Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian -Wei; Brashler, Kyle; Gustafson, Jeffrey A.; Huang, Wenyu

    2015-09-11

    Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic properties and thermal stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.

  13. Bimetallic nanostructures as active Raman markers: gold-nanoparticle assembly on 1D and 2D silver nanostructure surfaces.

    PubMed

    Gunawidjaja, Ray; Kharlampieva, Eugenia; Choi, Ikjun; Tsukruk, Vladimir V

    2009-11-01

    It is demonstrated that bimetallic silver-gold anisotropic nanostructures can be easily assembled from various nanoparticle building blocks with well-defined geometries by means of electrostatic interactions. One-dimensional (1D) silver nanowires, two-dimensional (2D) silver nanoplates, and spherical gold nanoparticles are used as representative building blocks for bottom-up assembly. The gold nanoparticles are electrostatically bound onto the 1D silver nanowires and the 2D silver nanoplates to give bimetallic nanostructures. The unique feature of the resulting nanostructures is the particle-to-particle interaction that subjects absorbed analytes to an enhanced electromagnetic field with strong polarization dependence. The Raman activity of the bimetallic nanostructures is compared with that of the individual nanoparticle blocks by using rhodamine 6G solution as the model analyte. The Raman intensity of the best-performing silver-gold nanostructure is comparable with the dense array of silver nanowires and silver nanoplates that were prepared by means of the Langmuir-Blodgett technique. An optimized design of a single-nanostructure substrate for surface-enhanced Raman spectroscopy (SERS), based on a wet-assembly technique proposed here, can serve as a compact and low-cost alternative to fabricated nanoparticle arrays.

  14. Plasmonic Properties of Bimetallic Nanostructures and Their Applications in Hydrogen Sensing and Chemical Reactions

    NASA Astrophysics Data System (ADS)

    Jiang, Ruibin

    Noble metal nanocrystals have attracted great interest from a wide range of research fields because of their intriguing properties endowed by their localized surface plasmon resonances, which are the collective oscillations of free electrons. Under resonant excitation, metal nanostructures exhibit very large scattering and absorption cross sections and large near-field enhancement. These extraordinary properties can be used in different applications, such as plasmonic sensing and imaging, plasmon-controlled optics, photothermal therapy, photocatalysis, solar cells, and so on. Gold and Silver nanocrystals have plasmon resonances in the visible and near-infrared regions. However, gold and silver are not suitable for some applications. For example, they are generally inactive for catalyzing chemical reactions. The integration of plasmonic metals with other metals can offer superior or new physical/chemical properties. In this thesis, I prepared Au/Ag and Au/Pd bimetallic nanostructures and studied their plasmonic properties and applications in hydrogen sensing and photocatalysis. Seeds have a crucial importance in the synthesis of bimetallic nanostructures. I therefore first studied the roles of the crystalline structure and shape of seeds on the overgrowth of bimetallic nanostructures. The overgrowth of silver and palladium on single crystalline Au nanorods, multicrystalline Au nanorods, and nanobipyramids were studied under the same conditions for each metal. The growths of silver and palladium on single crystalline Au nanorods gave cuboidal nanostructures, while rod-shaped nanostructures were obtained from the growths of silver and palladium on multicrystalline Au nanorods and nanobipyramids. Moreover, the growths of silver and palladium on multicrystalline Au nanobipyramids started at the stepped side facets, while the growths started at the twin boundaries on multicrystalline Au nanorods. These results unambiguously indicate that the crystalline structure of

  15. Controlling Bimetallic Nanostructures by the Microemulsion Method with Subnanometer Resolution Using a Prediction Model.

    PubMed

    Buceta, David; Tojo, Concha; Vukmirovic, Miomir B; Deepak, Francis Leonard; López-Quintela, M Arturo

    2015-07-14

    We present a theoretical model to predict the atomic structure of Au/Pt nanoparticles synthesized in microemulsions. Excellent concordance with the experimental results shows that the structure of the nanoparticles can be controlled at subnanometer resolution simply by changing the reactant concentration. The results of this study not only offer a better understanding of the complex mechanisms governing reactions in microemulsions, but open up a simple new way to synthesize bimetallic nanoparticles with ad hoc controlled nanostructures.

  16. NHC-Ag/Pd-Catalyzed Reductive Carboxylation of Terminal Alkynes with CO2 and H2 : A Combined Experimental and Computational Study for Fine-Tuned Selectivity.

    PubMed

    Yu, Dingyi; Zhou, Feng; Lim, Diane S W; Su, Haibin; Zhang, Yugen

    2017-03-09

    Reductive carboxylation of terminal alkynes utilizing CO2 and H2 as reactants is an interesting and challenging transformation. Theoretical calculations indicated it would be kinetically possible to obtain cinnamic acid, the reductive carboxylation product, from phenylacetylene in a CO2 /H2 system with an N-heterocyclic carbene (NHC)-supported Ag/Pd bimetallic catalysts through competitive carboxylation/hydrogenation cascade reactions in one step. These calculations were verified experimentally with a poly-NHC-supported Ag/Pd catalyst. By tuning the catalyst composition and reaction temperature, phenylacetylene was selectively converted to cinnamic acid, hydrocinnamic acid, or phenylpropiolic acid in excellent yields.

  17. Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures

    DOE PAGES

    Zarick, Holly F.; Erwin, William R.; Boulesbaa, Abdelaziz; ...

    2016-01-25

    In this paper, we demonstrate improved light trapping in dye-sensitized solar cells (DSSCs) with hybrid bimetallic gold core/silver shell nanostructures. Silica-coated bimetallic nanostructures (Au/Ag/SiO2 NSs) integrated in the active layer of DSSCs resulted in 7.51% power conversion efficiency relative to 5.97% for reference DSSCs, giving rise to 26% enhancement in device performance. DSSC efficiencies were governed by the particle density of Au/Ag/SiO2 NSs with best performing devices utilizing only 0.44 wt % of nanostructures. We performed transient absorption spectroscopy of DSSCs with variable concentrations of Au/Ag/SiO2 NSs and observed an increase in amplitude and decrease in lifetime with increasing particlemore » density relative to reference. Finally, we attributed this trend to plasmon resonant energy transfer and population of the singlet excited states of the sensitizer molecules at the optimum concentration of NSs promoting enhanced exciton generation and rapid charge transfer into TiO2.« less

  18. Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures

    SciTech Connect

    Zarick, Holly F.; Erwin, William R.; Boulesbaa, Abdelaziz; Hurd, Olivia K.; Webb, Joseph A.; Puretzky, Alexander A.; Geohegan, David B.; Bardhan, Rizia

    2016-01-25

    In this paper, we demonstrate improved light trapping in dye-sensitized solar cells (DSSCs) with hybrid bimetallic gold core/silver shell nanostructures. Silica-coated bimetallic nanostructures (Au/Ag/SiO2 NSs) integrated in the active layer of DSSCs resulted in 7.51% power conversion efficiency relative to 5.97% for reference DSSCs, giving rise to 26% enhancement in device performance. DSSC efficiencies were governed by the particle density of Au/Ag/SiO2 NSs with best performing devices utilizing only 0.44 wt % of nanostructures. We performed transient absorption spectroscopy of DSSCs with variable concentrations of Au/Ag/SiO2 NSs and observed an increase in amplitude and decrease in lifetime with increasing particle density relative to reference. Finally, we attributed this trend to plasmon resonant energy transfer and population of the singlet excited states of the sensitizer molecules at the optimum concentration of NSs promoting enhanced exciton generation and rapid charge transfer into TiO2.

  19. Controlling bimetallic nanostructures by the microemulsion method with subnanometer resolution using a prediction model

    SciTech Connect

    Buceta, David; Tojo, Concha; Vukmirovic, Miomir B.; Deepak, F. Leonard; Lopez-Quintela, M. Arturo

    2015-06-02

    In this study, we present a theoretical model to predict the atomic structure of Au/Pt nanoparticles synthesized in microemulsions. Excellent concordance with the experimental results shows that the structure of the nanoparticles can be controlled at sub-nanometer resolution simply by changing the reactants concentration. The results of this study not only offer a better understanding of the complex mechanisms governing reactions in microemulsions, but open up a simple new way to synthesize bimetallic nanoparticles with ad-hoc controlled nanostructures.

  20. Asymmetric AgPd-AuNR heterostructure with enhanced photothermal performance and SERS activity.

    PubMed

    Zhang, Han; Liu, Zeke; Kang, Xiaolin; Guo, Jun; Ma, Wanli; Cheng, Si

    2016-01-28

    Most as-reported nanostructures through galvanic replacement reactions are still symmetric hollow structures, until now. Asymmetric structures fabricated through a galvanic replacement reaction have been rarely reported. However, asymmetric heterostructures can generally lead to new intriguing properties through asymmetric synergistic coupling. Here, we report a simple synthesis of an asymmetric one-ended AgPd bimetal on Au nanorods (AuNR) by combining a galvanic replacement reaction with an Ostwald ripening process. The morphological evolution from a nanodumbbell to a dandelion structure is thoroughly investigated. The unique asymmetric AgPd-AuNR heterostructures possess the required plasmonic performance and avoid strong damping caused by the poor plasmonic metal Pd, resulting in a superior photothermal heating performance and enhanced SERS sensitivity for in situ monitoring of a catalytic reaction compared with the symmetric counterparts.

  1. Electron and Phonon Dynamics in Hexagonal Pd Nanosheets and Ag/Pd/Ag Sandwich Nanoplates.

    PubMed

    Wang, Li; Sagaguchi, Takuya; Okuhata, Tomoki; Tsuboi, Motohiro; Tamai, Naoto

    2017-02-28

    Pd and its hybrid nanostructures have attracted considerable attention over the past decade, with both catalytic and plasmonic properties. The electron and phonon properties directly govern conversion efficiencies in applications such as energy collectors and photocatalysts. We report the dynamic processes of electron-phonon coupling and coherent acoustic phonon vibration in hexagonal Pd nanosheets and Ag/Pd/Ag sandwich nanoplates using transient absorption spectroscopy. The electron-phonon coupling constant of Pd nanosheets, GPd-nanosheet (8.7 × 10(17) W/(m(3)·K)) is larger than that of the bulk GPd (5.0 × 10(17) W/(m(3)·K)). The effective coupling constant Geff of Ag/Pd/Ag nanoplates decreases with increasing Ag shell thickness, finally approaching the bulk GAg. The variation of Geff is explained in terms of reduced density of states near Fermi level of Pd nanosheets with 1.8 nm ultrathin thickness. Coherent acoustic phonon vibration in Pd nanosheets is assigned to a fundamental breathing mode, similar to the vibration of benzene. The period increases with increasing Ag shell thickness. For Ag/Pd/Ag nanoplates with 20 nm thick Ag shells, the vibrational mode is ascribed to a quasi-extensional mode. The results show that the modes of the coherent acoustic phonon vibration transform with the geometric variation of Pd nanosheets and Ag/Pd/Ag nanoplates. Our results represent an understanding of quantum-confinement related electron dynamics and bulk-like phonon kinetics in the ultrathin Pd nanosheets and their hybrid nanostructures.

  2. Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites.

    PubMed

    Zarick, Holly F; Boulesbaa, Abdelaziz; Puretzky, Alexander A; Talbert, Eric M; DeBra, Zachary R; Soetan, Naiya; Geohegan, David B; Bardhan, Rizia

    2017-01-26

    In this work, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr3) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3 perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.

  3. A photoactive bimetallic framework for direct aminoformylation ...

    EPA Pesticide Factsheets

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditions. The entwined AgPd@g-C3N4 catalyst was very effective in exploiting formic acid as a source of hydrogen and acting as a formylating agent under photochemical conditions. Prepared for submission to Royal Society of Chemistry (RSC) journal, Green Chemistry

  4. Insight into the Catalytic Mechanism of Bimetallic Platinum–Copper Core–Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions

    SciTech Connect

    Ma, Lu; Luo, Xiangyi; Kropf, A. Jeremy; Wen, Jianguo; Wang, Xiaoping; Lee, Sungsik; Myers, Deborah J.; Miller, Dean; Wu, Tianpin; Lu, Jun; Amine, Khalil

    2016-01-01

    The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt–Cu core–shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li–O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt–Cu core–shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

  5. A photoactive bimetallic framework for direct aminoformylation of nitroarenes

    EPA Science Inventory

    A bimetallic catalyst, AgPd@g-C3N4, was synthesized by immobilizing silver and palladium nanoparticles over the surface of graphitic carbon nitride (g-C3N4) and its utility was demonstrated for the concerted aminoformylation of aromatic nitro compounds under visible light conditi...

  6. Hollow Ag@Pd core-shell nanotubes as highly active catalysts for the electro-oxidation of formic acid.

    PubMed

    Jiang, Yuanyuan; Lu, Yizhong; Han, Dongxue; Zhang, Qixian; Niu, Li

    2012-03-16

    Ag nanowires are prepared as templates by a polyol reduction process. Then Ag nanotubes coated with a thin layer of Pd are synthesized through sequential reduction accompanied with the galvanic displacement reaction. The products show a hollow core-shell nanotubular structure, as demonstrated by detailed characterizations. The Ag@Pd can significantly improve the electrocatalytic activity towards the electro-oxidation of formic acid and enhance the stability of the Pd component. It is proposed that the enhanced electrochemically active surface area and modulated electron structure of Pd by Ag are responsible for the improvement of electrocatalytic activity and durability. The results obtained in this work are different from those previous reports, in which alloy walls with hollow interiors are usually formed. This work provides a new and simple method for synthesizing novel bimetallic core-shell structure with a hollow interior, which can be applied as high-performance catalysts for the electro-oxidation of formic acid.

  7. Study of Chemistry and Structure-Property Relationship on Tunable Plasmonic Nanostructures

    NASA Astrophysics Data System (ADS)

    Jing, Hao

    -resolved plasmon-enhanced spectroscopic measurements, such as surface-enhanced Raman scattering (SERS). Last but not least, I have demonstrated that the capability of geometry control over Ag-Pd bimetallic hollow nanostructures through nanoscale galvanic replacement can be greatly enhanced by the use of appropriate mild reducing agents, such as ascorbic acid and formaldehyde. With the aid of mild reducing agents, we have been able to fine-tailor the compositions, interior architectures, and surface morphologies of Ag-Pd bimetallic hollow nanoparticles with increased structural complexity through surface ligand-free galvanic replacement processes at room temperature. This reducing agent-mediated galvanic replacement provides a unique way of achieving both enhanced optical tunability and optimized catalytic activities through deliberate control over the geometries of complex Ag-Pd bimetallic nanoparticles.

  8. Inhibition of carbon monoxide on methanol oxidation over γ-alumina supported Ag, Pd and Ag Pd catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Jin-an; Aguilar-Ríos, G.; Wang, Ren

    1999-05-01

    The activities of CH 3OH and CO oxidative reactions over the γ-alumina supported Ag, Pd and Ag-Pd catalysts were measured with the MR-GC method. The CO-temperature-programmed desorption (CO-TPD) and in situ IR techniques were used to characterize the CO adsorption behavior on the surface of the catalysts. The oxidative activity for CO to CO 2 increased in the following sequence: 5% Ag/γ-Al 2O 3<0.1% Pd/γ-Al 2O 3<5% Ag-0.1% Pd/γ-Al 2O 3. An inhibition action of CO to CH 3OH oxidation, that is dependent of the active components of the catalysts, was observed when CO was present in the methanol-fed stream. The results of IR and CO-TPD showed that the poor oxidative activity of CO over Ag catalyst was due to its low adsorption capacity on this catalyst. The very strong adsorption ability of CO on the Pd catalyst was responsible for the strong inhibition of CO to CH 3OH oxidation activity. The plausible mechanisms of CO strong inhibition behavior on methanol oxidation over the different catalysts are discussed in detail from the viewpoints of both electronic and geometric effects.

  9. Fabrication of ultra-thin nanostructured bimetallic foils by Accumulative Roll Bonding and Asymmetric Rolling

    PubMed Central

    Yu, Hailiang; Lu, Cheng; Tieu, A. Kiet; Godbole, Ajit; Su, Lihong; Sun, Yong; Liu, Mao; Tang, Delin; Kong, Charlie

    2013-01-01

    This paper reports a new technique that combines the features of Accumulative Roll Bonding (ARB) and Asymmetric Rolling (AR). This technique has been developed to enable production of ultra-thin bimetallic foils. Initially, 1.5 mm thick AA1050 and AA6061 foils were roll-bonded using ARB at 200°C, with 50% reduction. The resulting 1.5 mm bimetallic foil was subsequently thinned to 0.04 mm through four AR passes at room temperature. The speed ratio between the upper and lower AR rolls was 1:1.3. The tensile strength of the bimetallic foil was seen to increase with reduction in thickness. The ductility of the foil was seen to reduce upon decreasing the foil thickness from 1.5 mm to 0.14 mm, but increase upon further reduction in thickness from 0.14 mm to 0.04 mm. The grain size was about 140 nm for the AA6061 layer and 235 nm for the AA1050 layer, after the third AR pass. PMID:23918002

  10. Graphene/nano-porous silicon and graphene/bimetallic silicon nanostructures (Pt-M, M: Pd, Ru, Rh), efficient electrocatalysts for the hydrogen evolution reaction.

    PubMed

    Ensafi, Ali A; Jafari-Asl, Mehdi; Rezaei, Behzad

    2015-10-07

    In this work nano-porous silicon flour (Nano-PSiF) was synthesized first and then there was an investigation into its electrocatalytic activity for the electrochemical hydrogen evolution reaction (HER). The results showed that Nano-PSiF has good electrocatalytic activity for the HER when compared with PSiF. In the second section, Pt and Pt-M (M = Pd, Rh, Ru) bimetallic silicon nanostructures were prepared by a direct reduction of the metal (Pt, Pt-Pd, Pt-Rh and Pt-Ru) on the surface of the PSiF by a galvanic exchange mechanism. The electrocatalytic activity of the bimetallic silicon nanostructures (Pt-M/PSiF) were evaluated for the HER. The results showed that all of the Pt-M/PSiFs have excellent electrocatalytic activity for the HER in a 0.5 mol L(-1) H2SO4 solution. For the Pt/PSiF, the Tafel slope of Pt/PSiF was 46.9 mV dec(-1), indicating its excellent electrocatalytic activity for the HER and it is comparable with commercial Pt/C. On the other hand, the bimetallic silicon nanostructures showed better electrocatalytic activity than Pt/PSiF for the HER (lower Tafel slope, and higher α). Finally, exfoliated graphene oxide was electro-deposited on the surface of a glassy carbon electrode (eRGO/GCE) and used as a sub-layer for the Pt-M/PSiF. Then, the electrocatalytic activities of the bimetallic silicon nanostructures on the eRGO/GCE were investigated for the HER. The results showed that there was a higher electrocatalytic activity for Pt-M/PSiF-eRGO/GCE when compared with Pt-M/PSiF-GCE.

  11. [Mechanical properties of wiredrawn Ag-Pd-Cu alloys].

    PubMed

    Hasegawa, T; Miyagawa, Y; Nakamura, K

    1989-01-01

    Nine experimental Ag-Pd-Cu ternary alloys, containing 20-30 wt% Pd and 10-20 wt% Cu, were cast into rods 4.5 mm in diameter using an original vacuum/argon-pressure oxide-free casting technique. Test samples 2.0 mm in diameter were made from the rods by wire-drawing. After softening and hardening heat treatments, mechanical properties (modulus of elasticity, elastic limit, proof stress, tensile strength, elongation, and Vickers hardness) of the samples were measured to analyze the effects of composition and fifteen sets of correlations between the mechanical properties on the condition that few internal casting defects existed. After softening heat treatment, values of hardness and strength increased with increasing Cu and Pd contents, while they increased approximately with increasing Pd content after hardening heat treatment. After softening and hardening heat treatments, tensile strength ranged from 44.4 to 60.7 and from 68.1 to 89.1 kgf/mm2, respectively. Values of elongation were more than 10% even after hardening heat treatment. Fourteen out of fifteen correlation coefficients (r) were statistically significant (p less than 0.01). One of the regression lines derived was as follows. Tensile strength (kgf/mm2) = 9.1 +/- 0.305 Hv (r = 0.990) Moreover, the mechanical properties observed in this investigation were compared with those of ordinarily cast samples with the same compositions.

  12. Studies on polishing of Ti and Ag-Pd-Cu-Au alloy with five dental abrasives.

    PubMed

    Hirata, T; Nakamura, T; Takashima, F; Maruyama, T; Taira, M; Takahashi, J

    2001-08-01

    Titanium (Ti) and Ag-Pd-Cu-Au alloy were examined for their polishing behaviour by conducting manually controlled polishing tests using five dental abrasives [carborundum point (CR) and silicone points (R1 and R2)] driven by a high torque micromotor with rotational speeds ranging from 2000 to 15 000 r.p.m. Polishing of Ti resulted in less volume of removal upon polishing, a rougher surface and larger loss of abrasives, compared with polishing of Ag-Pd-Cu-Au alloy. Polishing of Ti with a rotational speed of 15 000 r.p.m. led to the largest volume of removal upon polishing, whilst that of 10 000 r.p.m. produced the optimal volume for Ag-Pd-Cu-Au alloy. It was concluded that Ti was much more difficult to polish, requiring special care (e.g. frequent exchange of abrasives). Development of new abrasives for polishing Ti is required.

  13. Deformation-induced nanoscale mixing reactions in Cu/Ni and Ag/Pd multilayers

    SciTech Connect

    Wang, Z.; Perepezko, J. H.

    2013-11-04

    During the repeated cold rolling of Cu/Ni and Ag/Pd multilayers, a solid solution forms at the interfaces as nanoscale layer structure with a composition that replicates the overall multilayer composition. The interfacial mixing behavior was investigated by means of X-ray diffraction and scanning transmission electron microscopy. During deformation induced reaction, the intermixing behavior of the Cu/Ni and Ag/Pd multilayers is in contrast to thermally activated diffusion behavior. This distinct behavior can provide new kinetic pathways and offer opportunities for microstructure control that cannot be achieved by thermal processing.

  14. M-Au/TiO2 (M = Ag, Pd, and Pt) nanophotocatalyst for overall solar water splitting: role of interfaces

    NASA Astrophysics Data System (ADS)

    Melvin, Ambrose A.; Illath, Kavya; Das, Tanmay; Raja, Thirumalaiswamy; Bhattacharyya, Somnath; Gopinath, Chinnakonda S.

    2015-08-01

    M-Au/TiO2 (M = Ag, Pd, Pt) composites were prepared through a facile one-pot photodeposition synthesis and evaluated for solar water splitting (SWS) with and without a sacrificial agent. The M-Au combination exhibits a dominant role in augmenting the H2 generation activity by forming a bi-metallic system. Degussa P25 was used as a TiO2 substrate to photodeposit Au followed by Au + M (M = Ag/Pd/Pt). The SWS activity of the M-Au/TiO2 was determined through photocatalytic H2 production in the presence of methanol as a sacrificial agent under one sun conditions with an AM1.5 filter. The highest H2 yield was observed for Pt0.5-Au1/TiO2 and was around 1.3 +/- 0.07 mmol h-1 g-1, with an apparent quantum yield (AQY) of 6.4%. Pt0.5-Au1/TiO2 also demonstrated the same activity for 25 cycles of five hours each for 125 h. Critically, the same Pt0.5-Au1/TiO2 catalyst was active in overall SWS (OSWS) without any sacrificial agent, with an AQY = 0.8%. The amount of Au and/or Pt was varied to obtain the optimum composition and it was found that the Pt0.5-Au1/TiO2 composition exhibits the best activity. Detailed characterization by physico-chemical, spectral and microscopy measurements was carried out to obtain an in-depth understanding of the origin of the photocatalytic activity of Pt0.5-Au1/TiO2. These in-depth studies show that gold interacts predominantly with oxygen vacancies present on titania surfaces, and Pt preferentially interacts with gold for an effective electron-hole pair separation at Pt-Au interfaces and electron storage in metal particles. The Pt in Pt0.5-Au1/TiO2 is electronically and catalytically different from the Pt in Pt/TiO2 and it is predicted that the former suppresses the oxygen reduction reaction.M-Au/TiO2 (M = Ag, Pd, Pt) composites were prepared through a facile one-pot photodeposition synthesis and evaluated for solar water splitting (SWS) with and without a sacrificial agent. The M-Au combination exhibits a dominant role in augmenting the H2

  15. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    PubMed Central

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  16. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-04-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction.

  17. Nanoparticles alloying in liquids: Laser-ablation-generated Ag or Pd nanoparticles and laser irradiation-induced AgPd nanoparticle alloying.

    PubMed

    Semaltianos, N G; Chassagnon, R; Moutarlier, V; Blondeau-Patissier, V; Assoul, M; Monteil, G

    2017-04-18

    Laser irradiation of a mixture of single-element micro/nanomaterials may lead to their alloying and fabrication of multi-element structures. In addition to the laser induced alloying of particulates in the form of micro/nanopowders in ambient atmosphere (which forms the basis of the field of additive manufacturing technology), another interesting problem is the laser-induced alloying of a mixture of single-element nanoparticles in liquids since this process may lead to the direct fabrication of alloyed-nanoparticle colloidal solutions. In this work, bare-surface ligand-free Ag and Pd nanoparticles in solution were prepared by laser ablation of the corresponding bulk target materials, separately in water. The two solutions were mixed and the mixed solution was laser irradiated for different time durations in order to investigate the laser-induced nanoparticles alloying in liquid. Nanoparticles alloying and the formation of AgPd alloyed nanoparticles takes place with a decrease of the intensity of the surface-plasmon resonance peak of the Ag nanoparticles (at ∼405 nm) with the irradiation time while the low wavelength interband absorption peaks of either Ag or Pd nanoparticles remain unaffected by the irradiation for a time duration even as long as 30 min. The nanoalloys have lattice constants with values between those of the pure metals, which indicates that they consist of Ag and Pd in an approximately 1:1 ratio similar to the atomic composition of the starting mixed-nanoparticle solution. Formation of nanoparticle networks consisting of bimetallic alloyed nanoparticles and nanoparticles that remain as single elements (even after the end of the irradiation), joining together, are also formed. The binding energies of the 3d core electrons of both Ag and Pd nanoparticles shift to lower energies with the irradiation time, which is also a typical characteristic of AgPd alloyed nanoparticles. The mechanisms of nanoparticles alloying and network formation are also

  18. Nanoparticles alloying in liquids: Laser-ablation-generated Ag or Pd nanoparticles and laser irradiation-induced AgPd nanoparticle alloying

    NASA Astrophysics Data System (ADS)

    Semaltianos, N. G.; Chassagnon, R.; Moutarlier, V.; Blondeau-Patissier, V.; Assoul, M.; Monteil, G.

    2017-04-01

    Laser irradiation of a mixture of single-element micro/nanomaterials may lead to their alloying and fabrication of multi-element structures. In addition to the laser induced alloying of particulates in the form of micro/nanopowders in ambient atmosphere (which forms the basis of the field of additive manufacturing technology), another interesting problem is the laser-induced alloying of a mixture of single-element nanoparticles in liquids since this process may lead to the direct fabrication of alloyed-nanoparticle colloidal solutions. In this work, bare-surface ligand-free Ag and Pd nanoparticles in solution were prepared by laser ablation of the corresponding bulk target materials, separately in water. The two solutions were mixed and the mixed solution was laser irradiated for different time durations in order to investigate the laser-induced nanoparticles alloying in liquid. Nanoparticles alloying and the formation of AgPd alloyed nanoparticles takes place with a decrease of the intensity of the surface-plasmon resonance peak of the Ag nanoparticles (at ∼405 nm) with the irradiation time while the low wavelength interband absorption peaks of either Ag or Pd nanoparticles remain unaffected by the irradiation for a time duration even as long as 30 min. The nanoalloys have lattice constants with values between those of the pure metals, which indicates that they consist of Ag and Pd in an approximately 1:1 ratio similar to the atomic composition of the starting mixed-nanoparticle solution. Formation of nanoparticle networks consisting of bimetallic alloyed nanoparticles and nanoparticles that remain as single elements (even after the end of the irradiation), joining together, are also formed. The binding energies of the 3d core electrons of both Ag and Pd nanoparticles shift to lower energies with the irradiation time, which is also a typical characteristic of AgPd alloyed nanoparticles. The mechanisms of nanoparticles alloying and network formation are also

  19. Femtosecond Circular Photon Drag Effect in the Ag/Pd Nanocomposite

    NASA Astrophysics Data System (ADS)

    Mikheev, Gennady M.; Saushin, Aleksandr S.; Vanyukov, Viatcheslav V.; Mikheev, Konstantin G.; Svirko, Yuri P.

    2017-01-01

    We report on the observation of the helicity-dependent photoresponse of the 20-μm-thick silver-palladium (Ag/Pd) nanocomposite films. In the experiment, 120 fs pulses of Ti:S laser induced in the film an electric current perpendicular to the incidence plane. The photoinduced current is a linear function of the incident beam power, and its sign depends on the beam polarization and angle of incidence. In particular, the current is zero for the p- and s-polarized beams, while its sign is opposite for the right- and left-circularly polarized beams. By comparing experimental results with theoretical analysis, we show that the photoresponse of the Ag/Pd nanocomposite originates from the photon drag effect.

  20. Catalytic activity of nanostructured Au: Scale effects versus bimetallic/bifunctional effects in low-temperature CO oxidation on nanoporous Au

    PubMed Central

    Wang, Lu-Cun; Zhong, Yi; Jin, Haijun; Widmann, Daniel; Weissmüller, Jörg

    2013-01-01

    Summary The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure–activity correlations) and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG) samples prepared from different Au alloys (AuAg, AuCu) by selective leaching of a less noble metal (Ag, Cu) were employed, whose structure (surface area, ligament size) as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP) reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed. PMID:23503603

  1. AuAg bimetallic nonalloyed nanoparticles on a periodically nanostructured GaAs substrate for enhancing light trapping.

    PubMed

    Lee, Soo Kyung; Tan, Chee Leong; Ju, Gun Wu; Song, Jae Hong; Yeo, Chan Il; Lee, Yong Tak

    2015-12-15

    We present a light trapping structure consisting of AuAg bimetallic nonalloyed nanoparticles (BNNPs) on cone-shaped GaAs subwavelength structures (SWSs), combining the advantages of plasmonic structures and SWSs for GaAs-based solar cell applications. To obtain efficient light trapping in solar cells, the optical properties' dependence on the size and composition of the Ag and Au metal nanoparticles was systematically investigated. Cone-shaped GaAs SWSs with AuAg BNNPs formed from an Au film of 12 nm and an Ag film of 10 nm exhibited the extremely low average reflectance (R(avg)) of 2.43% and the solar-weighted reflectance (SWR) of 2.38%, compared to that of a bare GaAs substrate (R(avg), 37.50%; SWR, 36.72%) in the wavelength range of 300 to 870 nm.

  2. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  3. An electrochemical and multispectroscopic study of corrosion of Ag-Pd-Cu-Au alloys.

    PubMed

    Niemi, L; Minni, E; Ivaska, A

    1986-06-01

    Corrosion of a multi-phase Ag-Pd-Cu-Au-based commercial dental casting alloy and a Cu-Pd-rich and Ag-rich single-phase alloy was studied by open-circuit potential measurements, atomic absorption spectrometry, and electron spectroscopy. The alloys were immersed in an artificial saliva solution for 24 hr while the open-circuit potentials of the alloys were measured. The potentials were found to stabilize at certain levels after a steep rise during the first hours of the experiment. Cu was found to dissolve considerably from the Cu-Pd-rich alloy, with simultaneous enrichment of Pd in the surface layer of the alloy. Ag dissolved slightly from the Ag-rich alloy, but both Cu and Ag were found to dissolve from the multi-phase alloy. Neither Pd nor Au dissolved from any of the alloys studied.

  4. [Corrosion of Ag-Pd-Cu alloys in saline solution. Amount of released elements and electrochemical corrosion].

    PubMed

    Kitaoka, M

    1989-03-01

    The effect of the Pd content on corrosion and tarnish resistance in twelve experimental alloys was investigated. The alloys were prepared with a composition of Pd content from 20.1 to 30.1 at %. The composition of the alloys Ag-20% Pd, Ag-25% Pd and Ag-30% Pd was varied by adding Cu 5 wt%, 10 wt% and 15 wt% to each of them. The corrosion resistance was estimated by the amount of the released Ag, Cu and by electrochemical corrosion behavior in 0.86% NaCl solution at 37 degrees C. The tarnish resistance was assessed using a spectrophotometer. The test solutions included 0.86% NaCl solution, 0.1% Na2S solution and a mixture of 1.0% lactic acid and 0.1% Na2S, all at 37 degrees C, in sealed containers. The results are summarized as follows. The larger the amount of Pd in Ag-Pd binary alloys and Ag-Pd-Cu ternary alloys, the more stable was the release and the release rate of Ag, Cu and corrosion resistance increased in 0.86% NaCl solution. The addition of Cu to Ag-Pd binary alloys increased the release and release rate of Ag, but there was a shift of the rest potential in the noble direction. A relationship was found between the amount of Ag and Cu released from Ag-Pd-Cu ternary alloys. In this study, an increase in corrosion resistance was observed when the content of Pd in Ag-Pd binary alloys was 25 wt%. Furthermore, it was also observed that Ag-Pd-Cu ternary alloys need an additional 30 wt% Pd for corrosion resistance. Moreover, the addition of Cu must be kept lower than 10 wt%. The tarnish resistance of the twelve experimental alloys was good in 0.86% NaCl solution but was barely improved with increased in the Pd content in sulfide solution. The correlation between electrochemical corrosion behavior and tarnish resistance was not significant, but the correlation between the amount of Ag, Cu release from Ag-Pd-Cu ternary alloys and tarnish resistance was remarkable.

  5. Balance of Nanostructure and Bimetallic Interactions in Pt Model Fuel Cell Catalysts: An in Situ XAS and DFT Study

    SciTech Connect

    Friebel, Daniel; Viswanathan, Venkatasubramanian; Miller, Daniel James; Anniyev, Toyli; Ogasawara, Hirohito; Larsen, Ask Hjorth; O'Grady, Christopher P.; Norskov, Jens K.; Nilsson, Anders

    2012-05-31

    We have studied the effect of nanostructuring in Pt monolayer model electrocatalysts on a Rh(111) single-crystal substrate on the adsorption strength of chemisorbed species. In situ high energy resolution fluorescence detection X-ray absorption spectroscopy at the Pt L(3) edge reveals characteristic changes of the shape and intensity of the 'white-line' due to chemisorption of atomic hydrogen (H(ad)) at low potentials and oxygen-containing species (O/OH(ad)) at high potentials. On a uniform, two-dimensional Pt monolayer grown by Pt evaporation in ultrahigh vacuum, we observe a significant destabilization of both H(ad) and O/OH(ad) due to strain and ligand effects induced by the underlying Rh(111) substrate. When Pt is deposited via a wet-chemical route, by contrast, three-dimensional Pt islands are formed. In this case, strain and Rh ligand effects are balanced with higher local thickness of the Pt islands as well as higher defect density, shifting H and OH adsorption energies back toward pure Pt. Using density functional theory, we calculate O adsorption energies and corresponding local ORR activities for fcc 3-fold hollow sites with various local geometries that are present in the three-dimensional Pt islands.

  6. Development of Ag-Pd-Au-Cu alloys for multiple dental applications. Part 2. Mechanical properties of experimental Ag-Pd-Au-Cu alloys containing Sn or Ga for ceramic-metal restorations.

    PubMed

    Goto, S; Nakai, A; Miyagawa, Y; Ogura, H

    2001-06-01

    Eighteen Ag-Pd-Au-Cu alloys, consisting of nine Ag-Pd-Au-Cu mother compositions (Pd: 20, 30 or 40%, Au: 20%, Cu: 10, 15 or 20%, Ag: balance) containing either 5% Sn or 5% Ga as an additive metal, were experimentally prepared. Tensile strength, proof stress, elongation, elastic modulus, and Vickers hardness of these alloys were evaluated to clarify the potential of these alloys for use as ceramic-metal restorations as well as the effects of the Pd and Cu contents on their mechanical properties. The tensile strength, proof stress, elongation, elastic modulus and Vickers hardness of the 18 experimental alloys were in the range of 410.0-984.0 MPa, 289.7-774.3 MPa, 2.2-23.7%, 81.3-123.0 GPa and 135.7-332.3 HV1, respectively. Ten of the 18 experimental alloys can be used for ultra-low fusing ceramics based on their proof stress, elastic modulus, elongation and hardness. Between the Ga- and Sn-added alloys, differences in tensile strength, proof stress, elongation and hardness were found at several Ag-Pd-Au-Cu compositions.

  7. Transparent ITO/Ag-Pd-Cu/ITO multilayer cathode use in inverted organic solar cells

    SciTech Connect

    Kim, Hyo-Joong; Kim, Han-Ki; Lee, Hyun Hwi; Kal, Jinha; Hahn, Jungseok

    2015-10-15

    The characteristics of transparent ITO/Ag-Pd-Cu (APC)/ITO multilayer cathodes were investigated for use in inverted organic solar cells (IOSCs). The insertion of an APC interlayer into the ITO film effectively led to crystallization of the top ITO layer, unlike that in the Ag interlayer, and resulted in a low sheet resistance of 6.55 Ohm/square and a high optical transmittance of 84.14% without post annealing. In addition, the alloying of the Pd and Cu elements into Ag prevented agglomeration and oxidization of the metal interlayer and led to more stable ITO/APC/ITO films under ambient conditions. The microstructure and interfacial structure of the transparent ITO/APC/ITO cathode in the IOSCs were examined in detail by synchrotron X-ray scattering and high resolution transmission electron microscopy. Furthermore, we suggested a possible mechanism to explain the lower PCE of the IOSCs with an ITO/APC/ITO cathode than that of a reference IOSC with a crystalline ITO cathode using the external quantum efficiency of the IOSCs.

  8. Ag-Pd-Cu alloy inserted transparent indium tin oxide electrodes for organic solar cells

    SciTech Connect

    Kim, Hyo-Joong; Seo, Ki-Won; Kim, Han-Ki; Noh, Yong-Jin; Na, Seok-In

    2014-09-01

    The authors report on the characteristics of Ag-Pd-Cu (APC) alloy-inserted indium tin oxide (ITO) films sputtered on a glass substrate at room temperature for application as transparent anodes in organic solar cells (OSCs). The effect of the APC interlayer thickness on the electrical, optical, structural, and morphological properties of the ITO/APC/ITO multilayer were investigated and compared to those of ITO/Ag/ITO multilayer electrodes. At the optimized APC thickness of 8 nm, the ITO/APC/ITO multilayer exhibited a resistivity of 8.55 × 10{sup −5} Ω cm, an optical transmittance of 82.63%, and a figure-of-merit value of 13.54 × 10{sup −3} Ω{sup −1}, comparable to those of the ITO/Ag/ITO multilayer. Unlike the ITO/Ag/ITO multilayer, agglomeration of the metal interlayer was effectively relieved with APC interlayer due to existence of Pd and Cu elements in the thin region of the APC interlayer. The OSCs fabricated on the ITO/APC/ITO multilayer showed higher power conversion efficiency than that of OSCs prepared on the ITO/Ag/ITO multilayer below 10 nm due to the flatness of the APC layer. The improved performance of the OSCs with ITO/APC/ITO multilayer electrodes indicates that the APC alloy interlayer prevents the agglomeration of the Ag-based metal interlayer and can decrease the thickness of the metal interlayer in the oxide-metal-oxide multilayer of high-performance OSCs.

  9. Highly sensitive electrochemical sensing platform for lead ion based on synergetic catalysis of DNAzyme and Au-Pd porous bimetallic nanostructures.

    PubMed

    Zhou, Qian; Lin, Youxiu; Lin, Yuping; Wei, Qiaohua; Chen, Guonan; Tang, Dianping

    2016-04-15

    In this work, a sensitive and specific electrochemical biosensor for lead ion (Pb(2+)) detection was developed by coupling with synergetic catalysis of porous Au-Pd bimetallic nanoparticles and hemin/G-quadruplex-based DNAzyme. In the presence of target Pb(2+), the substrate strand was cleaved and the enzyme strand was released. Subsequently, G-rich DNA-labeled Au-Pd bimetallic nanoparticle was linked with the released enzyme strand through the helper DNA. Upon addition of hemin, a large number of hemin/G-quadruplex-based DNAzyme molecules were formed on the electrode to serve as nicotinamide adenine dinucleotide hydrogen (NADH) oxidase and peroxidase mimics. DNAzyme could catalyzed the reduction of H2O2, generated from NADH in the presence of O2, to produce an electrochemical signal when using thionine as the electron mediator. Introduction of porors Au-Pd bimetallic nanoparticles could enhance the detectable signal and cause the increase in the sensitivity. Experimental results showed that the variations (∆I) in the cathodic peak currents of the biosensor were linearly dependent on target Pb(2+) concentrations from 1.0 pM to 100 nM with a detection limit (LOD) of 0.34 pM. The excellent performance of the sensing platform indicated its promising prospect as a valuable tool for simple and cost-effective Pb(2+) detection in practical application.

  10. Hydrazine reduction of metal ions to porous submicro-structures of Ag, Pd, Cu, Ni, and Bi

    SciTech Connect

    Wang Yue; Shi Yongfang; Chen Yubiao; Wu Liming

    2012-07-15

    Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. Phase purity, morphology, and specific surface area have been characterized. The reactions probably undergo three different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. The reductant hydrazine also plays an important role to the formation of the porous submicro-structure. The reaction temperature influences the size of the constituent particles and the overall architecture of the submicro-structure so as to influence the surface area value. The as-prepared porous metals have shown the second largest surface area ever reported, which are smaller than those made by the reduction of NaBH{sub 4}, but larger than those made by hard or soft template methods. - Graphical abstract: Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in the glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. The reactions undergo different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. Highlights: Black-Right-Pointing-Pointer Syntheses of porous Ag, Pd, Cu, Ni, and Bi with high surface area. Black-Right-Pointing-Pointer Ag and Pd undergo simple reduction. Black-Right-Pointing-Pointer Cu and Ni undergo coordination-then-reduction. Black-Right-Pointing-Pointer Bi undergoes hydrolysis-then-reduction. Black-Right-Pointing-Pointer The as-prepared metals have shown the second largest surface area ever reported.

  11. Synthesis of nanostructured lean-NO x catalysts by direct laser deposition of monometallic Pt-, Rh- and bimetallic PtRh-nanoparticles on SiO2 support

    NASA Astrophysics Data System (ADS)

    Savastenko, N.; Volpp, H.-R.; Gerlach, O.; Strehlau, W.

    2008-02-01

    Monometallic Pt and Rh and bimetallic PtRh catalysts with a highly dispersed noble metal weight loading of ca. 1 wt% were produced via the direct deposition of nanoparticles on different SiO2 supports by means of pulsed ultra-violet (248 nm) excimer laser ablation of Pt, Rh bulk metal and PtRh alloy targets. Backscattered electron microscopy (BSE), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) were employed to characterize the deposited nanoparticles, which were found to exhibit narrow size distribution centred around 2.5 nm. The catalytic activities for lean NO x reduction of the monometallic and bimetallic catalyst samples were investigated in a flow reactor setup in the temperature range 100-400°C using a test gas mixture representative of oxygen rich diesel engine exhaust gas. For comparison a Rh/SiO2 reference catalyst prepared by a conventional impregnation method was also tested. Further experiments were performed in which PtRh nanoparticles were deposited on a Rh/SiO2 reference catalyst sample to study the possibility for controlled modification of its activity. The catalytic activity measurements revealed that among the samples solely prepared by laser deposition the PtRh-SiO2 nanoparticle catalyst showed the highest activity for NO x reduction at low temperatures 100-300°C. In addition, it could be demonstrated that the initially low NO x reduction activity and the N2 selectivity of the Rh/SiO2 reference catalyst sample for temperatures below 250°C can be enhanced by post laser deposition of PtRh nanoparticles.

  12. Ligand-controlled Co-reduction versus electroless Co-deposition: synthesis of nanodendrites with spatially defined bimetallic distributions.

    PubMed

    Ortiz, Nancy; Weiner, Rebecca G; Skrabalak, Sara E

    2014-12-23

    The predictable synthesis of bimetallic nanostructures via co-reduction of two metal precursors is challenging due to our limited understanding of precursor ligand effects. Here, the influence of different metal-ligand environments is systematically examined in the synthesis of Pd-Pt nanostructures as a model bimetallic system. Nanodendrites with different spatially defined Pd-Pt compositions are achieved, where the local ligand environments of metal precursors dictate if temporally separated co-reduction dominates to achieve core-shell nanostructures or whether electroless co-deposition proceeds to facilitate alloyed nanostructure formation. As the properties of bimetallic nanomaterials depend on crystal ordering and composition, chemical routes to structurally defined bimetallic nanomaterials are critically needed. The approaches reported here should be applicable to other bimetallic compositions given the established reactivity of coordination complexes available for use as precursors.

  13. The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO2 by radiolytic method

    NASA Astrophysics Data System (ADS)

    Klein, Marek; Nadolna, Joanna; Gołąbiewska, Anna; Mazierski, Paweł; Klimczuk, Tomasz; Remita, Hynd; Zaleska-Medynska, Adriana

    2016-08-01

    TiO2 (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM) and BET surface area analysis. The effect of metal type (mono- and bimetallic modification) as well as deposition method (simultaneous or subsequent deposition of two metals) on the photocatalytic activity in toluene removal in gas phase under UV-vis irradiation (light-emitting diodes- LEDs) and phenol degradation in liquid phase under visible light irradiation (λ > 420 nm) were investigated. The highest photoactivity under Vis light was observed for TiO2 co-loaded with platinum (0.1%) and palladium (0.1%) clusters. Simultaneous addition of metal precursors results in formation of larger metal nanoparticles (15-30 nm) on TiO2 surface and enhances the Vis-induced activity of Ag/Pd-TiO2 up to four times, while the subsequent metal ions addition results in formation of metal particle size ranging from 4 to 20 nm. Subsequent addition of metal precursors results in formation of BNPs (bimetallic nanoparticle) composites showing higher stability in four cycles of toluene degradation under UV-vis. Obtained results indicated that direct electron transfer from the BNPs to the conduction band of the semiconductor is responsible for visible light photoactivity, whereas superoxide radicals (such as O2rad- and rad OOH) are responsible for pollutants degradation over metal-TiO2 composites.

  14. Effect of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction of NOx with C2H5OH.

    PubMed

    Xie, Shu-xia; Yu, Yun-bo; Wang, Jin; He, Hong

    2006-01-01

    The influence of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction (SCR) of NOx with C2H5OH was investigated experimentally. The activity test results suggest that Ag-Pd/Al203 shows a small activity loss in the presence of SO2 when using C2H5OH as a reductant. In situ DRIFTS spectra show that the activity loss originates from the formation of surface sulphate species on the Ag-Pd/Al2O3. The surface sulphate species formation inhibits the formation of nitrate, whereas hardly changes the partial oxidation of C2HsOH. Compared with the NOx reduction by C3H6 an obvious suppression of the surface sulphate species formation was observed by DRIFTS experiment when using C2H50H as a reductant. This phenomenon reveals the better catalytic performance and strong SO2 tolerance of Ag-Pd/Al2O3-C2H5OH system.

  15. Structural and magnetic phase transitions in CeCu6-xTx (T = Ag,Pd)

    DOE PAGES

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; ...

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transitionmore » in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.« less

  16. Synthesis of nanostructured NiO/Co3O4 through thermal decomposition of a bimetallic (Ni/Co) metal-organic framework as catalyst for cyclooctene epoxidation

    NASA Astrophysics Data System (ADS)

    Abbasi, Alireza; Soleimani, Mohammad; Najafi, Mahnaz; Geranmayeh, Shokoofeh

    2017-04-01

    Hydrothermal approach has led to the formation of a three-dimensional metal-organic framework (MOF), [NiCo(μ2-tp)(μ4-tp)(4,4‧-bpy)2]n (1) (tp = terephthalic acid and 4,4‧-bpy = 4,4‧-bipyridine) which was characterized by means of single-crystal X-ray diffraction analysis, powder X-ray diffraction (PXRD), FT-IR spectroscopy, scanning electron microscopy (SEM) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Thermal decomposition of the MOF afforded nanostructured mixed metal oxide, namely NiO/Co3O4. The XRD and SEM analysis confirm the formation of the mixed metal oxide. The nanostructured NiO/Co3O4 demonstrated good catalytic activity and selectivity in the epoxidation of cyclooctene in the presence of tert-butyl hydroperoxide (TBHP) as oxidant.

  17. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions

    PubMed Central

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-01-01

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550

  18. Ag/Pd core-shell nanoparticles by a successive method: Pulsed laser ablation of Ag in water and reduction reaction of PdCl2

    NASA Astrophysics Data System (ADS)

    Mottaghi, N.; Ranjbar, M.; Farrokhpour, H.; Khoshouei, M.; Khoshouei, A.; Kameli, P.; Salamati, H.; Tabrizchi, M.; Jalilian-Nosrati, M.

    2014-02-01

    In this study Ag/Pd nanoparticles (NPs) have been fabricated by a successive method; first, colloids of Ag nanoparticles (NPs) have been prepared in water by pulsed laser ablation in liquid (PLAL) method. Then PdCl2 solution (up to 0.2 g/l) were added to the as-prepared or aged colloidal Ag NPs. Characterizations were done using UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmissions electron microscopy (TEM) techniques. Spectroscopy data showed that surface plasmon resonance (SPR) peaks of as-prepared Ag NPs at about λ = 400 nm were completely extinguished after addition of PdCl2 solution while this effect was not observed when aged Ag NPs are used. XRD and XPS results revealed that by addition of the PdCl2 solution into the as-prepared Ag NPs, metallic palladium, and silver chloride composition products are generated. TEM images revealed that as a result of this reaction, single and core-shell nanoparticles are obtained and their average sizes are 2.4 nm (Ag) and 3.2 nm (Ag/Pd). The calculated d-spacing values form XRD data with observations on high magnification TEM images were able to explain the chemical nature of different parts of Ag/Pd NPs.

  19. Biosensors Incorporating Bimetallic Nanoparticles

    PubMed Central

    Rick, John; Tsai, Meng-Che; Hwang, Bing Joe

    2015-01-01

    This article presents a review of electrochemical bio-sensing for target analytes based on the use of electrocatalytic bimetallic nanoparticles (NPs), which can improve both the sensitivity and selectivity of biosensors. The review moves quickly from an introduction to the field of bio-sensing, to the importance of biosensors in today’s society, the nature of the electrochemical methods employed and the attendant problems encountered. The role of electrocatalysts is introduced with reference to the three generations of biosensors. The contributions made by previous workers using bimetallic constructs, grouped by target analyte, are then examined in detail; following which, the synthesis and characterization of the catalytic particles is examined prior to a summary of the current state of endeavor. Finally, some perspectives for the future of bimetallic NPs in biosensors are given. PMID:28344262

  20. Plasmonic emission enhancement of colloidal quantum dots in the presence of bimetallic nanoparticles

    SciTech Connect

    Sadeghi, S. M.; Hatef, A.; Meunier, M.; Nejat, A.; Campbell, Q.

    2014-04-07

    We studied plasmonic features of bimetallic nanostructures consisting of gold nanoisland cores semi-coated with a chromium layer and explored how they influence emission of CdSe/ZnS quantum dots. We showed that, compared with chromium-covered glass substrates without the gold cores, the bimetallic nanostructures could significantly enhance the emission of the quantum dots. We studied the impact of the excitation intensity and thickness of the chromium layer on this process and utilized numerical means to identify the mechanisms behind it. Our results suggest that when the chromium layer is thin, the enhancement process is the result of the bimetallic plasmonic features of the nanostructures. As the chromium layer becomes thick, the impact of the gold cores is screened and the enhancement mostly happens mostly via the field enhancement of chromium nanoparticles in the absence of significant energy transfer from the quantum dots to these nanoparticles.

  1. Effect of additive metals, Sn, Ga, and In in Ag-Pd-Au-Cu alloys on initial bond strength of 4-META adhesive cement to these alloys.

    PubMed

    Goto, Shin-ichi; Churnjitapirom, Pornkiat; Miyagawa, Yukio; Ogura, Hideo

    2008-09-01

    The purpose of this study was to investigate the effects of three additives, Sn, Ga, and In, as well as the main constituents, Pd and Cu, of Ag-Pd-Au-Cu alloys on the initial bond strength of 4-META adhesive cement to these alloys. The Ag-Pd-Au-Cu alloys consisted of 20%, 30% or 40% Pd, and 10%, 15% or 20% Cu, 20% Au, and Ag as balance. Besides, additive metals (Sn, Ga, and In) of 2% and 4% were added to these compositions. The addition of three additives, in general, increased the initial bond strength of the cement in comparison to the mother compositions (0% additives), although the degrees of effectiveness of the three additives were different and varied with their contents. Among these additives, a remarkable increase in bond strength was observed with the addition of In. The increase in Cu content, in many cases, resulted in an increase in bond strength at high Pd contents (30% and 40%), but a decrease at low Pd content (20%) in some cases. The positive effects of the three additives and Cu could be due to the formation of a suitable oxide layer for strong bonding with 4-META.

  2. In vitro study on the corrosion behavior of three commercial Ag-Pd-Cu-Au alloys in Ringer's and 0.1%Na2S solutions.

    PubMed

    Endo, K; Araki, Y; Kawashima, I; Yamane, Y; Ohno, H; Matsuda, K

    1989-12-01

    The corrosion resistance of three commercial Ag-Pd-Cu-Au alloys was estimated in Ringer's and 0.1% Na2S solutions by electrochemical techniques and surface analyses. In Ringer's solution, the three alloys showed high corrosion resistance and there was no significant difference in the anodic polarization characteristics of the three alloys. In the 0.1% Na2S solution, the Alloy A which had the lowest noble metal content (Au + Pd) exhibited the highest anodic reactivity with the largest amount of corrosion product on the alloy surface. It was determined that the Ag-rich phase of Ag-Pd-Cu-Au alloy was preferentially attacked to form Ag2S corrosion product. The polarization resistance data showed that the corrosion rate for Alloy A in 0.1% Na2S solution was determined to be 500 times higher than that in Ringer's solution. The corrosion rate of the alloy in the freely corroded condition can be estimated quantitatively and precisely by measuring the polarization resistance.

  3. Confinement effects on the shape and composition of bimetallic nano-objects in carbon nanotubes.

    PubMed

    Li, X; Hungria, T; Garcia Marcelot, C; Axet, M R; Fazzini, P-F; Tan, R P; Serp, P; Soulantica, K

    2016-02-07

    CoPt and FePt nanostructures have been efficiently confined in carbon nanotubes (CNTs). A marked confinement effect has been evidenced, both on bimetallic nano-object shape and composition. In large diameter CNTs small Co- and Fe-rich nanoparticles are formed, while in small diameter CNTs Pt-rich nanowires are selectively produced.

  4. Structural and magnetic phase transitions in CeCu6-xTx (T = Ag,Pd)

    SciTech Connect

    Poudel, Lekhanath N.; De la cruz, Clarina; Payzant, E. Andrew; Koehler, Michael R.; May, Andrew F.; Garlea, Vasile O.; Taylor, Alice E.; Parker, David S.; Cao, Huibo B.; McGuire, Michael A.; Tian, Wei; Matsuda, Masaaki; Jeen, Hyoung Jeen; Lee, Ho Nyung; Hong, Tao; Calder, Stuart A.; Lumsden, Mark D.; Zhou, Haidong; Keppens, Veerle; Mandrus, D.; Christianson, Andrew D.

    2015-12-15

    The structural and the magnetic properties of CeCu6-xAgx (0 ≤ x ≤ 0.85) and CeCu6-xPdx (0 ≤ x ≤ 0.4) have been studied using neutron diffraction, resonant ultrasound spectroscopy (RUS), x-ray diffraction measurements, and first principles calculations. The structural and magnetic phase diagrams of CeCu6-xAgx and CeCu6-xPdx as a function of Ag/Pd composition are reported. The end member, CeCu6, undergoes a structural phase transition from an orthorhombic (Pnma) to a monoclinic (P21/c) phase at 240 K. In CeCu6-xAgx, the structural phase transition temperature (Ts) decreases linearly with Ag concentration and extrapolates to zero at xS ≈ 0.1. The structural transition in CeCu6-xPdx remains unperturbed with Pd substitution within the range of our study. The lattice constant b slightly decreases with Ag/Pd doping, whereas a and c increase with an overall increase in the unit cell volume. Both systems, CeCu6-xAgx and CeCu6-xPdx, exhibit a magnetic quantum critical point (QCP), at x ≈ 0.2 and x ≈ 0.05, respectively. Near the QCP, long range antiferromagnetic ordering takes place at an incommensurate wave vector (δ1 0 δ2), where δ1 ~ 0.62, δ2 ~ 0.25, x = 0.125 for CeCu6-xPdx and δ1 ~ 0.64, δ2 ~ 0.3, x = 0.3 for CeCu6-xAgx. As a result, the magnetic structure consists of an amplitude modulation of the Ce moments which are aligned along the c axis of the orthorhombic unit cell.

  5. Aptamer-guided silver-gold bimetallic nanostructures with highly active surface-enhanced Raman scattering for specific detection and near-infrared photothermal therapy of human breast cancer cells.

    PubMed

    Wu, Ping; Gao, Yang; Zhang, Hui; Cai, Chenxin

    2012-09-18

    The aptamer (S2.2)-guided Ag-Au nanostructures (aptamer-Ag-Au) have been synthesized by photoreduction and validated by ultraviolet-visible light (UV-vis) spectra and transmission electron microscopy (TEM) images. Differential interference contrast (DIC), fluorescence, and TEM images, and surface-enhanced Raman scattering (SERS) spectra indicated that the aptamer-Ag-Au nanostructures can target the surface of human breast cancer cells (MCF-7) with high affinity and specificity. This targeting is completed via the specific interaction between S2.2 aptamer (a 25-base oligonucleotide) and MUC1 mucin (a large transmembrane glycoprotein, whose expression increased at least 10-fold at MCF-7 cells in primary and metastatic breast cancers). However, the nanostructures cannot target HepG2 (human liver cancer cells) or MCF-10A cells (human normal breast epithelial cells), because these cells are MUC1-negative expressed. Moreover, the synthesized nanostructures exhibited a high SERS activity. Based on these results, a new assay for specifically detecting MCF-7 cells has been proposed. This assay can also discriminate MCF-7 cells from MCF-10A cells and different cancer cell lines, such as HepG2 cells. In addition, the aptamer-Ag-Au nanostructures have a high capability of adsorpting near-infrared (NIR) irradiation and are able to perform photothermal therapy of MCF-7 cells at a very low irradiation power density (0.25 W/cm(2)) without destroying the healthy cells and the surrounding normal tissue. Therefore, the proposed assay is significant for the diagnosis of tumors in their nascent stage. The synthesized nanostructures could offer a protocol to specifically recognize and sensitively detect the cancer cells, and would have great potential for application in the photothermal therapy of the cancers.

  6. Catalytically active designer crown-jewel Pd-based nanostructures encapsulated in metal-organic frameworks.

    PubMed

    Chen, Liyu; Huang, Weihao; Wang, Xiujun; Chen, Zhijie; Yang, Xianfeng; Luque, Rafael; Li, Yingwei

    2017-01-17

    A series of crown-jewel Pd-based bimetallic nanostructures with tunable composition are fabricated inside the pores of an MOF via a hydride-induced-reduction strategy, exhibiting high activity and stability in the hydrogenation of nitrobenzene.

  7. Enzymatic plasmonic engineering of Ag/Au bimetallic nanoshells and their use for sensitive optical glucose sensing.

    PubMed

    He, Haili; Xu, Xiaolong; Wu, Haoxi; Jin, Yongdong

    2012-04-03

    Enzyme works for plasmonic nanostructure: an interesting enzyme-responsive hybrid Ag/Au-GOx bimetallic nanoshell (NS) system is reported, in which control over the enzyme reaction of glucose oxidase (GOx) can automatically fine-tune the morphology (from complete NS to porous NS) and optical properties of the hybrid nanostructure. The phenomenon is further exploited as a new platform for sensitive optical glucose sensing.

  8. Optical properties and sensing applications of stellated and bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Smith, Alison F.

    This dissertation focuses on developing guidelines to aid in the design of new bimetallic platforms for sensing applications. Stellated metal nanostructures are a class of plasmonic colloids in which large electric field enhancements can occur at sharp features, making them excellent candidates for surface enhanced Raman spectroscopy (SERS) and surface enhanced infrared spectroscopy (SE-IRS) platforms. Shape-dependent rules for convex polyhedra such as cubes or octahedra exist, which describe far-field scattering and near-field enhancements. However, such rules are lacking for their concave (stellated) counterparts. This dissertation presents the optical response of stellated Au nanocrystals with Oh, D4h, D3h, C2v, and T d symmetry, which were modeled to systematically investigate the role of symmetry, branching, and particle orientation with respect to excitation source using finite difference time domain (FDTD) calculations. Expanding on stellated nanostructures, bimetallic compositions introduce an interplay between overall architecture and composition to provide tunable optical properties and the potential of new functionality. However, decoupling the complex compositional and structural contributions to the localized surface plasmon resonance (LSPR) remains a challenge, especially when the monometallic counterparts are not synthetically accessible for comparison and the theoretical tools for capturing gradient compositions are lacking. This dissertation explores a stellated Au-Pd nanocrystal model system with Oh symmetry to decouple structural and complex compositional effects on LSPR. (Abstract shortened by ProQuest.).

  9. Plasmon-induced broadband fluorescence enhancement on Al-Ag bimetallic substrates

    NASA Astrophysics Data System (ADS)

    Hao, Qi; Du, Deyang; Wang, Chenxi; Li, Wan; Huang, Hao; Li, Jiaqi; Qiu, Teng; Chu, Paul K.

    2014-08-01

    Surface enhanced fluorescence (SEF) utilizes the local electromagnetic environment to enhance fluorescence from the analyte on the surface of a solid substrate with nanostructures. While the detection sensitivity of SEF is improved with the development of nano-techniques, detection of multiple analytes by SEF is still a challenge due to the compromise between the high enhancing efficiency and broad response bandwidth. In this article, a high-efficiency SEF substrate with broad response bandwidth is obtained by embedding silver in an aluminum film to produce additional bonding and anti-bonding hybridized states. The bimetallic film is fabricated by ion implantation and the ion energy and fluence are tailored to control subsurface location of the fabricated bimetallic nanostructures. The process circumvents the inherent limit of aluminum materials and extends the plasmon band of aluminum from deep UV to visible range. Fluorescence from different dyes excited by 310 nm to 555 nm is enhanced by up to 11 folds on the single bimetallic film and the result is theoretically confirmed by finite-difference time-domain simulations. This work demonstrates that bimetallic film can be used for optical detection of multiple analytes.

  10. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  11. Bimetallic nanoparticles for arsenic detection.

    PubMed

    Moghimi, Nafiseh; Mohapatra, Mamata; Leung, Kam Tong

    2015-06-02

    Effective and sensitive monitoring of heavy metal ions, particularly arsenic, in drinking water is very important to risk management of public health. Arsenic is one of the most serious natural pollutants in soil and water in more than 70 countries in the world. The need for very sensitive sensors to detect ultralow amounts of arsenic has attracted great research interest. Here, bimetallic FePt, FeAu, FePd, and AuPt nanoparticles (NPs) are electrochemically deposited on the Si(100) substrate, and their electrochemical properties are studied for As(III) detection. We show that trace amounts of As(III) in neutral pH could be determined by using anodic stripping voltammetry. The synergistic effect of alloying with Fe leads to better performance for Fe-noble metal NPs (Au, Pt, and Pd) than pristine noble metal NPs (without Fe alloying). Limit of detection and linear range are obtained for FePt, FeAu, and FePd NPs. The best performance is found for FePt NPs with a limit of detection of 0.8 ppb and a sensitivity of 0.42 μA ppb(-1). The selectivity of the sensor has also been tested in the presence of a large amount of Cu(II), as the most detrimental interferer ion for As detection. The bimetallic NPs therefore promise to be an effective, high-performance electrochemical sensor for the detection of ultratrace quantities of arsenic.

  12. Laser deposition of bimetallic island films

    NASA Astrophysics Data System (ADS)

    Kucherik, A. O.; Arakelyan, S. M.; Kutrovskaya, S. V.; Osipov, A. V.; Istratov, A. V.; Vartanyan, T. A.; Itina, T. E.

    2016-08-01

    In this work the results of a bimetallic Au-Ag structure deposition from the colloidal system by nanosecond laser radiation are presented. The formation of the extended arrays of gold and silver nanoparticles with controlled morphology is examined. We report the results of formation bimetallic islands films with various electrical and optical properties. The changes in the optical properties of the obtained thin films are found to depend on their morphology.

  13. Homogeneous Pt-bimetallic Electrocatalysts

    SciTech Connect

    Wang, Chao; Chi, Miaofang; More, Karren Leslie; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Alloying has shown enormous potential for tailoring the atomic and electronic structures, and improving the performance of catalytic materials. Systematic studies of alloy catalysts are, however, often compromised by inhomogeneous distribution of alloying components. Here we introduce a general approach for the synthesis of monodispersed and highly homogeneous Pt-bimetallic alloy nanocatalysts. Pt{sub 3}M (where M = Fe, Ni, or Co) nanoparticles were prepared by an organic solvothermal method and then supported on high surface area carbon. These catalysts attained a homogeneous distribution of elements, as demonstrated by atomic-scale elemental analysis using scanning transmission electron microscopy. They also exhibited high catalytic activities for the oxygen reduction reaction (ORR), with improvement factors of 2-3 versus conventional Pt/carbon catalysts. The measured ORR catalytic activities for Pt{sub 3}M nanocatalysts validated the volcano curve established on extended surfaces, with Pt{sub 3}Co being the most active alloy.

  14. Effect of Au thickness on AuAg bimetallic growth on reconstructed Si(5 5 12) surfaces

    NASA Astrophysics Data System (ADS)

    Bhukta, Anjan; Ghosh, Arnab; Guha, Puspendu; Maiti, Paramita; Satpati, Biswarup; Satyam, Parlapalli Venkata

    2017-03-01

    Large, stable and single domain unit cell with row-like structures makes reconstructed Si(5 5 12) surface an important one-dimensional growth template of nanostructures. We report on the morphological aspects of the growth of AuAg bimetallic nanostructures on a reconstructed Si(5 5 12) surface that has been deposited with a 0.5 monolayer (ML) Ag and various Au thicknesses (0.5 to 5.0 ML) to determine the optimum gold thickness for a growth of high aspect ratio of AuAg nanostructures. The mean aspect ratio of AuAg nanostructures increases up to Au thickness of 3.0 ML and for larger thickness the mean aspect ratio decreases. The prior growth of 0.5 ML Ag on reconstructed surface result in the formation of one-dimensional Ag strips which are helping for preferential nucleation sites along Si< 1bar{1}0 rangle to form AuAg bimetallic long aspect ratio structures. Followed by these early processes of growth, for Au thickness >3.0 ML, excess Au ad-atoms begin to accumulate along Si< 66bar{5} rangle and consequences reduction of mean aspect ratio of bimetallic nanostructures. Nanostructures are grown using molecular beam epitaxy method under ultra-high vacuum conditions and in situ scanning tunneling microscopy has been used to investigate the morphological variations. Determination of structural aspects and compositional analysis has been carried out using Rutherford backscattering spectrometry and high-resolution (scanning) transmission electron microscopy methods.

  15. Facile One-Step Synthesis of Three-Dimensional Pd-Ag Bimetallic Alloy Networks and Their Electrocatalytic Activity toward Ethanol Oxidation.

    PubMed

    Fu, Shaofang; Zhu, Chengzhou; Du, Dan; Lin, Yuehe

    2015-07-01

    The three-dimensional palladium networks and palladium-silver bimetallic alloy networks were synthesized at room temperature on a large scale using a rapid and simple strategy. The results revealed that the morphology of the networks is not affected by the composition. We demonstrated that the as-prepared unsupported networks exhibited excellent electrochemical activity and stability toward ethanol oxidation reaction in alkaline media due to the formation of palladium-silver alloys as well as the porous nanostructures. The results indicate that the well-defined three-dimensional palladium-silver bimetallic alloy networks are promising catalysts for fuel cells.

  16. Plasmonic effects of au/ag bimetallic multispiked nanoparticles for photovoltaic applications.

    PubMed

    Sharma, Manisha; Pudasaini, Pushpa Raj; Ruiz-Zepeda, Francisco; Vinogradova, Ekaterina; Ayon, Arturo A

    2014-09-10

    In recent years, there has been considerable interest in the use of plasmons, that is, free electron oscillations in conductors, to boost the performance of both organic and inorganic thin film solar cells. This has been driven by the possibility of employing thin active layers in solar cells in order to reduce materials costs, and is enabled by significant advances in fabrication technology. The ability of surface plasmons in metallic nanostructures to guide and confine light in the nanometer scale has opened up new design possibilities for solar cell devices. Here, we report the synthesis and characterization of highly monodisperse, reasonably stable, multipode Au/Ag bimetallic nanostructures using an inorganic additive as a ligand for photovoltaic applications. A promising surface enhanced Raman scattering (SERS) effect has been observed for the synthesized bimetallic Au/Ag multispiked nanoparticles, which compare favorably well with their Au and Ag spherical nanoparticle counterparts. The synthesized plasmonic nanostructures were incorporated on the rear surface of an ultrathin planar c-silicon/organic polymer hybrid solar cell, and the overall effect on photovoltaic performance was investigated. A promising enhancement in solar cell performance parameters, including both the open circuit voltage (VOC) and short circuit current density (JSC), has been observed by employing the aforementioned bimetallic multispiked nanoparticles on the rear surface of solar cell devices. A power conversion efficiency (PCE) value as high as 7.70% has been measured in a hybrid device with Au/Ag multispiked nanoparticles on the rear surface of an ultrathin, crystalline silicon (c-Si) membrane (∼ 12 μm). This value compares well to the measured PCE value of 6.72% for a similar device without nanoparticles. The experimental observations support the hope for a sizable PCE increase, due to plasmon effects, in thin-film, c-Si solar cells in the near future.

  17. Fabrication of bimetallic Cu/Au nanotubes and their sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

    PubMed

    Tee, Si Yin; Ye, Enyi; Pan, Pei Hua; Lee, Coryl Jing Jun; Hui, Hui Kim; Zhang, Shuang-Yuan; Koh, Leng Duei; Dong, Zhili; Han, Ming-Yong

    2015-07-07

    Herein, we report a facile two-step approach to produce gold-incorporated copper (Cu/Au) nanostructures through controlled disproportionation of the Cu(+)-oleylamine complex at 220 °C to form copper nanowires and the subsequent reaction with Au(3+) at different temperatures of 140, 220 and 300 °C. In comparison with copper nanowires, these bimetallic Cu/Au nanostructures exhibit their synergistic effect to greatly enhance glucose oxidation. Among them, the shape-controlled Cu/Au nanotubes prepared at 140 °C show the highest electrocatalytic activity for non-enzymatic glucose sensing in alkaline solution. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to the initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

  18. Development of Ag-Pd-Au-Cu alloy for multiple dental applications. Part 1. Effects of Pd and Cu contents, and addition of Ga or Sn on physical properties and bond with ultra-low fusing ceramic.

    PubMed

    Goto, S; Miyagawa, Y; Ogura, H

    2000-09-01

    Ag-Pd-Au-Cu quaternary alloys consisting of 30-50% Ag, 20-40% Pd, 10-20% Cu and 20% Au (mother alloys) were prepared. Then 5% Sn or 5% Ga was added to the mother alloy compositions, and another two alloy systems (Sn-added alloys and Ga-added alloys) were also prepared. The bond between the prepared alloys and an ultra-low fusing ceramic as well as their physical properties such as the solidus point, liquidus point and the coefficient of thermal expansion were evaluated. The solidus point and liquidus point of the prepared alloys ranged from 802 degrees C to 1142 degrees C and from 931 degrees C to 1223 degrees C, respectively. The coefficient of thermal expansion ranged from 14.6 to 17.1 x 10(-6)/degrees C for the Sn- and Ga-added alloys. In most cases, the Pd and Cu contents significantly influenced the solidus point, liquidus point and coefficient of thermal expansion. All Sn- and Ga-added alloys showed high area fractions of retained ceramic (92.1-100%), while the mother alloy showed relatively low area fractions (82.3%) with a high standard deviation (20.5%). Based on the evaluated properties, six Sn-added alloys and four Ga-added alloys among the prepared alloys were suitable for the application of the tested ultra-low fusing ceramic.

  19. Green synthesis and applications of Au-Ag bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Meena Kumari, M.; Jacob, John; Philip, Daizy

    2015-02-01

    This paper reports for the first time the synthesis of bimetallic nanoparticles at room temperature using the fruit juice of pomegranate. Simultaneous reduction of gold and silver ions in different molar ratios leads to the formation of alloy as well as core-shell nanostructures. The nanoparticles have been characterized using UV-vis spectroscopy, transmission electron microscopy, Fourier Transform Infrared Spectroscopy and X-ray diffraction. The synthesized alloy particles are used as catalysts in the reduction of 2-, 3-, 4-nitrophenols to the corresponding amines and in the degradation of methyl orange. The reduction kinetics for all the reactions follows pseudo-first order. The rate constants follow the order k4-nitrophenol < k2-nitrophenol < k3-nitrophenol. Thermal conductivity is measured as a function of volume fraction and it is observed that the incorporation of the alloy nanoparticles enhances the thermal conductivity of the base fluid (water) showing nanofluid application. The nitric oxide and hydroxyl radical scavenging activity shown by the nanoparticles promise the potential application in biomedical field.

  20. Engineering Hybrid Metallic Nanostructures Using a Single Domain of Block Copolymer Templates.

    PubMed

    Liu, Zhicheng; Chang, Tongxin; Huang, Haiying; He, Tianbai

    2015-11-25

    Building complex nanostructures using a simple patterned template is challenging in material science and nanotechnology. In the present work, three different strategies have been exploited for the successful fabrication of hybrid dots-on-wire metallic nanostructures through combining an in-situ method with an ex-situ method. Basically, plasma etching was applied to generate a metallic wire-like nanostructure, and preformed nanoparticles could be placed through multiple means before or after the formation of the wire-like nanostructure. Various monometallic and bimetallic nanostructures have been obtained by utilizing only one functional domain of block copolymer templates. In these cases, full utilization of the functional domain or introduction of the molecular linker is critical to engineering hybrid metallic nanostructures. Other complex and multifunctional hybrid nanostructures can be developed via these strategies similarly, and these nanostructures are promising for useful applications such as optics and surface-enhanced Raman spectroscopy (SERS).

  1. Stainless Steel to Titanium Bimetallic Transitions

    SciTech Connect

    Kaluzny, J. A.; Grimm, C.; Passarelli, D.

    2015-01-01

    In order to use stainless steel piping in an LCLS-II (Linac Coherent Light Source Upgrade) cryomodule, stainless steel to titanium bimetallic transitions are needed to connect the stainless steel piping to the titanium cavity helium vessel. Explosion bonded stainless steel to titanium transition pieces and bimetallic transition material samples have been tested. A sample transition tube was subjected to tests and x-ray examinations between tests. Samples of the bonded joint material were impact and tensile tested at room temperature as well as liquid helium temperature. The joint has been used successfully in horizontal tests of LCLS-II cavity helium vessels and is planned to be used in LCLS-II cryomodules. Results of material sample and transition tube tests will be presented.

  2. Bimetallic redox synergy in oxidative palladium catalysis.

    PubMed

    Powers, David C; Ritter, Tobias

    2012-06-19

    Polynuclear transition metal complexes, which are embedded in the active sites of many metalloenzymes, are responsible for effecting a diverse array of oxidation reactions in nature. The range of chemical transformations remains unparalleled in the laboratory. With few noteworthy exceptions, chemists have primarily focused on mononuclear transition metal complexes in developing homogeneous catalysis. Our group is interested in the development of carbon-heteroatom bond-forming reactions, with a particular focus on identifying reactions that can be applied to the synthesis of complex molecules. In this context, we have hypothesized that bimetallic redox chemistry, in which two metals participate synergistically, may lower the activation barriers to redox transformations relevant to catalysis. In this Account, we discuss redox chemistry of binuclear Pd complexes and examine the role of binuclear intermediates in Pd-catalyzed oxidation reactions. Stoichiometric organometallic studies of the oxidation of binuclear Pd(II) complexes to binuclear Pd(III) complexes and subsequent C-X reductive elimination from the resulting binuclear Pd(III) complexes have confirmed the viability of C-X bond-forming reactions mediated by binuclear Pd(III) complexes. Metal-metal bond formation, which proceeds concurrently with oxidation of binuclear Pd(II) complexes, can lower the activation barrier for oxidation. We also discuss experimental and theoretical work that suggests that C-X reductive elimination is also facilitated by redox cooperation of both metals during reductive elimination. The effect of ligand modification on the structure and reactivity of binuclear Pd(III) complexes will be presented in light of the impact that ligand structure can exert on the structure and reactivity of binuclear Pd(III) complexes. Historically, oxidation reactions similar to those discussed here have been proposed to proceed via mononuclear Pd(IV) intermediates, and the hypothesis of mononuclear Pd

  3. PD/MG BIMETALLIC CORROSION CELLS FOR DECHLORINATING PCBS

    EPA Science Inventory

    Two dissimilar metals immersed in a conducting solution develop different corrosion potentials forming a bimetallic corrosion cell. Enhanced corrosion of an active metal like Mg combined with catalytic hydrogenation properties of a noble metal like Pd in such bimetallic cells can...

  4. Preparation of regular arrays of bimetallic clusters with independent control of size and chemical composition.

    PubMed

    Marsault, M; Hamm, G; Wörz, A; Sitja, G; Barth, C; Henry, C R

    2008-01-01

    Regular arrays of bimetallic clusters have been prepared by atomic deposition, under UHV, on a nanostructured ultrathin alumina film. The alumina films are obtained by oxidation at 1000 K of a Ni3Al (111) surface. They present two regular hexagonal superstructures with lattice parameters of 2.4 and 4.1 nm. Pd clusters nucleate exclusively on the 4.1 nm superstructure forming regular arrays of clusters extending on the whole (1 cm2) substrate. Gold deposited on a previously formed Pd clusters array, condenses exclusively on the Pd clusters in forming a regular array of bimetallic AuPd clusters with a narrow size distribution. The size and the composition of the AuPd clusters can be controlled independently. Gold clusters nucleates also on the 4.1 nm superstructure but they can escape from the nucleation sites and coalesce with other gold clusters. By condensing Pd on the preformed Au clusters, PdAu clusters are formed together with pure Pd clusters nucleated on the free sites of the 4.1 nm superstructure of the alumina film.

  5. Earth abundant bimetallic nanoparticles for heterogeneous catalysis

    NASA Astrophysics Data System (ADS)

    Senn, Jonathan F., Jr.

    Polymer exchange membrane fuel cells have the potential to replace current fossil fuel-based technologies in terms of emissions and efficiency, but CO contamination of H2 fuel, which is derived from steam methane reforming, leads to system inefficiency or failure. Solutions currently under development are bimetallic nanoparticles comprised of earth-abundant metals in different architectures to reduce the concentration of CO by PROX during fuel cell operation. Chapter One introduces the Pt-Sn and Co-Ni bimetallic nanoparticle systems, and the intermetallic and core-shell architectures of interest for catalytic evaluation. Application, theory, and studies associated with the efficacy of these nanoparticles are briefly reviewed. Chapter Two describes the concepts of the synthetic and characterization methods used in this work. Chapter Three presents the synthetic, characterization, and catalytic findings of this research. Pt, PtSn, PtSn2, and Pt 3Sn nanoparticles have been synthesized and supported on gamma-Al2O3. Pt3Sn was shown to be an effective PROX catalyst in various gas feed conditions, such as the gas mixture incorporating 0.1% CO, which displayed a light-off temperatures of ˜95°C. Co and Ni monometallic and CoNi bimetallic nanoparticles have been synthesized and characterized, ultimately leading to the development of target Co Ni core-shell nanoparticles. Proposed studies of catalytic properties of these nanoparticles in preferential oxidation of CO (PROX) reactions will further elucidate the effects of different crystallographic phases, nanoparticle-support interactions, and architecture on catalysis, and provide fundamental understanding of catalysis with nanoparticles composed of earth abundant metals in different architectures.

  6. Bimetallic nanoparticles: Preparation, properties, and biomedical applications.

    PubMed

    Nasrabadi, Hamid Tayefi; Abbasi, Elham; Davaran, Soodabeh; Kouhi, Mohammad; Akbarzadeh, Abolfazl

    2016-01-01

    Many studies of non-supported bimetallic nanoparticle (BMNP) dispersions, stabilized by ligands or polymers, and copolymers, were started only about 10 years ago. Several preparative procedures have been proposed, and full characterizations on BMNPs have been approved. Studies on BMNPs received huge attention from both scientific and technological communities because most of the NPs' catalytic activity depends on their structural aspects. In this study, we focus on the preparation, properties, and bio-application of BMNPs and introduction of the recent advance in these NPs.

  7. Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

    SciTech Connect

    Lim, B.; Tao, J.; Jiang, M.; Camargo, P.H.C.; Cho, E.C.; Lu, X.; Zhu, Y.; Xia, Y.

    2009-06-05

    Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K{sub 2}PtCl{sub 4} with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

  8. Gold-platinum bimetallic nanotubes templated from tellurium nanowires as efficient electrocatalysts for methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Lu, Chenchen; Kong, Wei; Zhang, Huying; Song, Bo; Wang, Zhenghua

    2015-11-01

    In this paper, gold-platinum (Au-Pt) bimetallic nanotubes with different Au/Pt ratio are successfully synthesized through a simple wet-chemical reduction route in which tellurium (Te) nanowires serve as both sacrificial template and reducing agent. The hollow nanostructure of Au-Pt nanotubes is formed due to Kirkendall effect. The as-prepared Au-Pt nanotubes can be applied as catalyst for methanol oxidation reaction, and the results indicate that the Au-Pt nanotubes with an Au/Pt ratio of 1:1 show the best electrochemical catalytic performances. Furthermore, the catalytic activity of the Au-Pt nanotubes is also better than Pt nanotubes and commercial Pt/C catalyst.

  9. BIMETALLIC LITHIUM BOROHYDRIDES TOWARD REVERSIBLE HYDROGEN STORAGE

    SciTech Connect

    Au, M.

    2010-10-21

    Borohydrides such as LiBH{sub 4} have been studied as candidates for hydrogen storage because of their high hydrogen contents (18.4 wt% for LiBH{sub 4}). Limited success has been made in reducing the dehydrogenation temperature by adding reactants such as metals, metal oxides and metal halides. However, full rehydrogenation has not been realized because of multi-step decomposition processes and the stable intermediate species produced. It is suggested that adding second cation in LiBH{sub 4} may reduce the binding energy of B-H. The second cation may also provide the pathway for full rehydrogenation. In this work, several bimetallic borohydrides were synthesized using wet chemistry, high pressure reactive ball milling and sintering processes. The investigation found that the thermodynamic stability was reduced, but the full rehydrogenation is still a challenge. Although our experiments show the partial reversibility of the bimetallic borohydrides, it was not sustainable during dehydriding-rehydriding cycles because of the accumulation of hydrogen inert species.

  10. @AuAg nanostructures

    NASA Astrophysics Data System (ADS)

    Singh, Rina; Soni, R. K.

    2014-09-01

    Bimetallic and trimetallic nanoparticles have attracted significant attention in recent times due to their enhanced electrochemical and catalytic properties compared to monometallic nanoparticles. The numerical calculations using Mie theory has been carried out for three-layered metal nanoshell dielectric-metal-metal (DMM) system consisting of a particle with a dielectric core (Al@Al2O3), a middle metal Ag (Au) layer and an outer metal Au (Ag) shell. The results have been interpreted using plasmon hybridization theory. We have also prepared Al@Al2O3@Ag@Au and Al@Al2O3@AgAu triple-layered core-shell or alloy nanostructure by two-step laser ablation method and compared with calculated results. The synthesis involves temporal separations of Al, Ag, and Au deposition for step-by-step formation of triple-layered core-shell structure. To form Al@Ag nanoparticles, we ablated silver for 40 min in aluminium nanoparticle colloidal solution. As aluminium oxidizes easily in water to form alumina, the resulting structure is core-shell Al@Al2O3. The Al@Al2O3 particle acts as a seed for the incoming energetic silver particles for multilayered Al@Al2O3@Ag nanoparticles is formed. The silver target was then replaced by gold target and ablation was carried out for different ablation time using different laser energy for generation of Al@Al2O3@Ag@Au core-shell or Al@Al2O3@AgAu alloy. The formation of core-shell and alloy nanostructure was confirmed by UV-visible spectroscopy. The absorption spectra show shift in plasmon resonance peak of silver to gold in the range 400-520 nm with increasing ablation time suggesting formation of Ag-Au alloy in the presence of alumina particles in the solution.

  11. Au-Pt bimetallic nanoparticles supported on nest-like MnO2: synthesis and application in HCHO decomposition

    NASA Astrophysics Data System (ADS)

    Yu, Xuehua; He, Junhui; Wang, Donghui; Hu, Yucai; Tian, Hua; Dong, Tongxin; He, Zhicheng

    2012-11-01

    Facile synthesis of Au-Pt bimetallic nanoparticles (Au1- x Pt x NPs) and mixtures of Au NPs and Pt NPs ((100 % - y)Au/ yPt NPs) and their subsequent deposition on nest-like MnO2 nanostructures were presented. The as-prepared products were characterized by means of UV-visible spectroscopy, X-ray diffraction, scanning and transmission electron microscopy, and energy dispersive spectroscopy. TEM analyses showed that noble metal NPs were evenly dispersed on the surface of nest-like MnO2 nanostructures and no agglomeration was observed. The as-prepared metal NPs supported catalysts showed higher catalytic activities than MnO2 nanostructures for oxidative decomposition of formaldehyde (HCHO). The forms of noble metal NPs and Au/Pt molar ratio have significant effects on the catalytic performance, and Au0.5Pt0.5/MnO2 has the highest catalytic activity among all the as-prepared metal NPs supported MnO2 catalysts, and the temperature for complete decomposition of HCHO reached as low as 313 K. The high catalytic activities of Au1- x Pt x /MnO2 catalysts resulted from the synergistic effect between Au1- x Pt x NPs and MnO2 nanostructure, as well as the synergistic effect between Au and Pt. The current Au1- x Pt x /MnO2 catalysts are among the first trials to apply bimetallic NP-supported catalysts to the decomposition of HCHO, and proved that the Au1- x Pt x /MnO2 catalysts are promising for indoor decomposition of formaldehyde due to their easy synthesis, low cost, and excellent catalytic performance.

  12. Superhydrophilic nanostructure

    DOEpatents

    Mao, Samuel S; Zormpa, Vasileia; Chen, Xiaobo

    2015-05-12

    An embodiment of a superhydrophilic nanostructure includes nanoparticles. The nanoparticles are formed into porous clusters. The porous clusters are formed into aggregate clusters. An embodiment of an article of manufacture includes the superhydrophilic nanostructure on a substrate. An embodiment of a method of fabricating a superhydrophilic nanostructure includes applying a solution that includes nanoparticles to a substrate. The substrate is heated to form aggregate clusters of porous clusters of the nanoparticles.

  13. Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

    DOEpatents

    Marks, Tobin J [Evanston, IL; Rodriguez, Brandon A [Evanston, IL; Delferro, Massimiliano [Chicago, IL

    2012-08-07

    A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

  14. Bimetallic Microswimmers Speed Up in Confining Channels

    NASA Astrophysics Data System (ADS)

    Liu, Chang; Zhou, Chao; Wang, Wei; Zhang, H. P.

    2016-11-01

    Synthetic microswimmers are envisioned to be useful in numerous applications, many of which occur in tightly confined spaces. It is therefore important to understand how confinement influences swimmer dynamics. Here we study the motility of bimetallic microswimmers in linear and curved channels. Our experiments show swimmer velocities increase, up to 5 times, with the degree of confinement, and the relative velocity increase depends weakly on the fuel concentration and ionic strength in solution. Experimental results are reproduced in a numerical model which attributes the swimmer velocity increase to electrostatic and electrohydrodynamic boundary effects. Our work not only helps to elucidate the confinement effect of phoretic swimmers, but also suggests that spatial confinement may be used as an effective control method for them.

  15. Gold over Branched Palladium Nanostructures for Photothermal Cancer Therapy.

    PubMed

    McGrath, Andrew J; Chien, Yi-Hsin; Cheong, Soshan; Herman, David A J; Watt, John; Henning, Anna M; Gloag, Lucy; Yeh, Chen-Sheng; Tilley, Richard D

    2015-12-22

    Bimetallic nanostructures show exciting potential as materials for effective photothermal hyperthermia therapy. We report the seed-mediated synthesis of palladium-gold (Pd-Au) nanostructures containing multiple gold nanocrystals on highly branched palladium seeds. The nanostructures were synthesized via the addition of a gold precursor to a palladium seed solution in the presence of oleylamine, which acts as both a reducing and a stabilizing agent. The interaction and the electronic coupling between gold nanocrystals and between palladium and gold broadened and red-shifted the localized surface plasmon resonance absorption maximum of the gold nanocrystals into the near-infrared region, to give enhanced suitability for photothermal hyperthermia therapy. Pd-Au heterostructures irradiated with an 808 nm laser light caused destruction of HeLa cancer cells in vitro, as well as complete destruction of tumor xenographs in mouse models in vivo for effective photothermal hyperthermia.

  16. Metal nanostructures for non-enzymatic glucose sensing.

    PubMed

    Tee, Si Yin; Teng, Choon Peng; Ye, Enyi

    2017-01-01

    This review covers the recent development of metal nanostructures in electrochemical non-enzymatic glucose sensing. It highlights a variety of nanostructured materials including noble metals, other transition metals, bimetallic systems, and their hybrid with carbon-based nanomaterials. Particularly, attention is devoted to numerous approaches that have been implemented for improving the sensors performance by tailoring size, shape, composition, effective surface area, adsorption capability and electron-transfer properties. The correlation of the metal nanostructures to the glucose sensing performance is addressed with respect to the linear concentration range, sensitivity and detection limit. In overall, this review provides important clues from the recent scientific achievements of glucose sensor nanomaterials which will be essentially useful in designing better and more effective electrocatalysts for future electrochemical sensing industry.

  17. Thermal stability of bimetallic Au/Fe nanoparticles in silica matrix

    SciTech Connect

    Pannu, Compesh Singh, Udai B. Hooda, Sonu Kabiraj, D. Avasthi, D. K.

    2014-04-24

    Thin silica film containing Au and Fe bimetallic nanoparticles were prepared by atom beam cosputtering. The samples were annealed at different temperatures from 400 to 800° C to study the thermal stability of bimetallic nanoparticles using X ray diffraction. It is observed that at 800° C strong structural rearrangement took place leading to thermal decomposition of bimetallic nanoparticles.

  18. Degradation of chlorofluorocarbons using granular iron and bimetallic irons.

    PubMed

    Jeen, Sung-Wook; Lazar, Snezana; Gui, Lai; Gillham, Robert W

    2014-03-01

    Degradation of trichlorofluoromethane (CFC11) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) by granular iron and bimetallic (nickel- or palladium-enhanced) irons was studied in flow-through column tests. Both compounds were rapidly degraded, following pseudo-first-order kinetics with respect to the parent compounds. The average pseudo-first-order rate constants for CFC11 were similar among different materials, except for palladium-enhanced iron (PdFe), in which the rate of degradation was about two times faster than for the other materials. In the case of CFC113, the rate constants for bimetallic irons were about two to three times greater than for the regular iron material. The smaller than expected differences in degradation rate constants of chlorofluorocarbons (CFCs) between regular iron and bimetallic irons suggested little, if any, catalytic effect of the bimetallic materials in the initial degradation step. Subsequent degradation steps involved catalytic hydrogenation, however, playing a significant role in further degradation of reaction intermediates. The degradation intermediates and final products of CFC11 and CFC113 suggested that degradation proceeded through hydrogenolysis and α/β-elimination in the presence of regular iron (Fe) and nickel-enhanced iron (NiFe). Even though there is only minor benefit in the use of bimetallic iron in terms of degradation kinetics of the parent CFCs, enhanced degradation rates of intermediates such as chlorotriflouroethene (CTFE) in subsequent reaction steps could be beneficial.

  19. Nanostructured materials

    NASA Astrophysics Data System (ADS)

    Moriarty, Philip

    2001-03-01

    Nanostructured materials may be defined as those materials whose structural elements - clusters, crystallites or molecules - have dimensions in the 1 to 100 nm range. The explosion in both academic and industrial interest in these materials over the past decade arises from the remarkable variations in fundamental electrical, optical and magnetic properties that occur as one progresses from an `infinitely extended' solid to a particle of material consisting of a countable number of atoms. This review details recent advances in the synthesis and investigation of functional nanostructured materials, focusing on the novel size-dependent physics and chemistry that results when electrons are confined within nanoscale semiconductor and metal clusters and colloids. Carbon-based nanomaterials and nanostructures including fullerenes and nanotubes play an increasingly pervasive role in nanoscale science and technology and are thus described in some depth. Current nanodevice fabrication methods and the future prospects for nanostructured materials and nanodevices are discussed.

  20. Ag-Sn Bimetallic Catalyst with a Core-Shell Structure for CO2 Reduction.

    PubMed

    Luc, Wesley; Collins, Charles; Wang, Siwen; Xin, Hongliang; He, Kai; Kang, Yijin; Jiao, Feng

    2017-02-08

    Converting greenhouse gas carbon dioxide (CO2) to value-added chemicals is an appealing approach to tackle CO2 emission challenges. The chemical transformation of CO2 requires suitable catalysts that can lower the activation energy barrier, thus minimizing the energy penalty associated with the CO2 reduction reaction. First-row transition metals are potential candidates as catalysts for electrochemical CO2 reduction; however, their high oxygen affinity makes them easy to be oxidized, which could, in turn, strongly affect the catalytic properties of metal-based catalysts. In this work, we propose a strategy to synthesize Ag-Sn electrocatalysts with a core-shell nanostructure that contains a bimetallic core responsible for high electronic conductivity and an ultrathin partially oxidized shell for catalytic CO2 conversion. This concept was demonstrated by a series of Ag-Sn bimetallic electrocatalysts. At an optimal SnOx shell thickness of ∼1.7 nm, the catalyst exhibited a high formate Faradaic efficiency of ∼80% and a formate partial current density of ∼16 mA cm(-2) at -0.8 V vs RHE, a remarkable performance in comparison to state-of-the-art formate-selective CO2 reduction catalysts. Density-functional theory calculations showed that oxygen vacancies on the SnO (101) surface are stable at highly negative potentials and crucial for CO2 activation. In addition, the adsorption energy of CO2(-) at these oxygen-vacant sites can be used as the descriptor for catalytic performance because of its linear correlation to OCHO* and COOH*, two critical intermediates for the HCOOH and CO formation pathways, respectively. The volcano-like relationship between catalytic activity toward formate as a function of the bulk Sn concentration arises from the competing effects of favorable stabilization of OCHO* by lattice expansion and the electron conductivity loss due to the increased thickness of the SnOx layer.

  1. Bimetallic strip for low temperature use

    DOEpatents

    Bussiere, Jean F.; Welch, David O.; Suenaga, Masaki

    1981-01-01

    There is provided a class of mechanically pre-stressed structures, suitably bi-layer strips comprising a layer of group 5 transition metals in intimate contact with a layer of an intermetallic compound of said transition metals with certain group 3A, 4A or 5A metals or metalloids suitably gallium, indium, silicon, germanium, tin, arsenic or antimony. The changes of Young's modulus of these bi-layered combinations at temperatures in the region of but somewhat above absolute zero provides a useful means of sensing temperature changes. Such bi-metallic strips may be used as control strips in thermostats, in direct dial reading instruments, or the like. The structures are made by preparing a sandwich of a group 5B transition metal strip between the substantially thicker strips of an alloy between copper and a predetermined group 3A, 4A or 5A metal or metalloid, holding the three layers of the sandwich in intimate contact heating the same, cooling the same and removing the copper alloy and then removing one of the two thus formed interlayer alloys between said transition metal and the metal previously alloyed with copper.

  2. Synthesis of bimetallic nanoshells by an improved electroless plating method.

    PubMed

    Liu, J B; Dong, W; Zhan, P; Wang, S Z; Zhang, J H; Wang, Z L

    2005-03-01

    In the Letter, we demonstrate an improved electroless plating method for the synthesis of bimetallic shell particles. The procedure involves a combination of surface reaction, seeding growth, and removal of supporting cores. We modified ammonical AgNO3 in ethanol with a controlled amount of HCHO in the seeding process and a uniform and relatively dense coverage of silver nanoparticle seeds on colloid cores was achieved. Following the second kind of metal plating, we extended this method to prepare continuous bimetallic core-shell and hollow particles with a submicrometer diameter. The morphologies of the bimetallic Cu/Ag and Pt/Ag particles were studied with transmission electron microscopy and scanning electron microscopy, and their crystallinity and chemical composition were confirmed by X-ray diffraction. The prepared materials may be of applied value in areas such as catalysis, optics, and plasmonics.

  3. Structure-Property Relationship in Metal Carbides and Bimetallic Alloys

    SciTech Connect

    Chen, Jingguan

    2014-03-04

    The primary objective of our DOE/BES sponsored research is to use carbide and bimetallic catalysts as model systems to demonstrate the feasibility of tuning the catalytic activity, selectivity and stability. Our efforts involve three parallel approaches, with the aim at studying single crystal model surfaces and bridging the “materials gap” and “pressure gap” between fundamental surface science studies and real world catalysis. The utilization of the three parallel approaches has led to the discovery of many intriguing catalytic properties of carbide and bimetallic surfaces and catalysts. During the past funding period we have utilized these combined research approaches to explore the possibility of predicting and verifying bimetallic and carbide combinations with enhanced catalytic activity, selectivity and stability.

  4. Shape control of bimetallic nanocatalysts through well-designed colloidal chemistry approaches.

    PubMed

    Gu, Jun; Zhang, Ya-Wen; Tao, Franklin Feng

    2012-12-21

    Synthesis of bimetallic nanomaterials with well controlled shape is an important topic in heterogeneous catalysis, low-temperature fuel cell technology, and many other fields. Compared with monometallic counterparts, bimetallic nanocatalysts endow scientists with more opportunities to optimize the catalytic performance by modulating the charge transfer between different metals, local coordination environment, lattice strain and surface element distribution. Considering the current challenges in shape controlled synthesis of bimetallic nanocatalysts, this tutorial review highlights some significant achievements in preparing bimetallic alloy, core-shell and heterostructure nanocrystals with well-defined morphologies, summarizes four general routes and some key factors of the bimetallic shape control scenarios, and provides some general ideas on how to design synthetic strategies to control the shape and exposing facets of bimetallic nanocrystals. The composition and shape dependent catalytic behaviours of bimetallic nanocrystals are reviewed as well.

  5. Synthesis of monodispersed bimetallic palladium-copper nanoscale colloids

    SciTech Connect

    Bradley, J.S.; Hill, E.W.; Klein, C. ); Chaudret, B.; Duteil, A. )

    1993-03-01

    Bimetallic clusters have been the subject of many studies of the surface chemistry and catalytic properties of metal crystallites on solid supports. Mixtures of palladium acetate and copper acetate were refluxed in 2-ethoxyethanol in the presence of poly(vinylpyrrolidone) to give 40-[angstrom] alloy nanoclusters. TEM and EDAX analysis showed that the particles were homogeneously bimetallic and crystalline, with a composition determined by the ratio of the metal acetates used. Carbon monoxide adsorbed on the colloidal particles binds reversibly to both metals. 9 refs., 3 figs.

  6. Edgeless Ag-Pt Bimetallic Nanocages: In Situ Monitor Plasmon-Induced Suppression of Hydrogen Peroxide Formation.

    PubMed

    Lin, Sheng-Chih; Hsu, Chia-Shuo; Chiu, Shih-Yun; Liao, Tzu-Yu; Chen, Hao Ming

    2017-02-15

    Improvements in the performance of electrocatalysts, along with continuing advances in selective pathway for target reaction, have great potential to offer opportunities in designing competitive reactions especially for using a photophysical process owing to its tunable properties. Herein, we demonstrated a first empirical evidence of suppressing the formation of undesired peroxide intermediate through plasmonic effects, in which plasmonic Ag-Pt bimetallic nanocages were synthesized with an edgeless feature, and a custom-made RDE/RRDE working station was designed to provide unique means by which to in situ realize the plasmon-induced effects toward the target reaction. The edgeless Ag-Pt bimetallic nanocages with hollow interior performed newly plasmon-induced effects, which was characteristic of photodependent nature to suppress the formation of undesired peroxide intermediate. We concluded that the plasmon-induced hot electron transfer governed the suppression of peroxide formation instead of plasmon-induced heating that would cause a negative effect (i.e., increase of peroxide yield), in which the hot electron transfer of Ag nanostructure offered a sufficient energy to populate the antibonding orbital of O2 as illustrated by in situ X-ray absorption approach. This rapid light-dependent nature corresponding to localized surface plasmon resonance in present nanocages can potentially offer synergetic strategies toward altering the chemical reactions or reaction pathways in various fields.

  7. Spectroscopic Elucidation of First Steps of Supported Bimetallic Cluster Formation

    SciTech Connect

    Kulkarni, A.; Gates, B.C.

    2009-12-23

    Initial steps of bimetallic Ru-Os cluster formation on MgO in the presence of H{sub 2} are analyzed by EXAFS and IR spectroscopy. Ru-Os bond formation takes place after decarbonylation of Ru{sub 3} clusters and subsequently, at higher temperatures, of Os{sub 3} clusters to generate coordinative unsaturation.

  8. Lithium-tellurium bimetallic cell has increased voltage

    NASA Technical Reports Server (NTRS)

    Cairns, E. J.; Rogers, G. L.; Shimotake, H.

    1968-01-01

    Lithium-tellurium secondary cell with a fused lithium halide electrolyte, tested in the temperature range 467 degrees to 500 degrees C, showed improvement over the sodium bismuth cell. The voltage of this bimetallic cell was increased by using the more electropositive anode material, lithium, and the more electronegative cathode material, tellurium.

  9. Lattice measurement and alloy compositions in metal and bimetallic nanoparticles.

    PubMed

    Tsen, S-C Y; Crozier, P A; Liu, J

    2003-12-01

    A new reliable method for determining the lattice spacings of metallic and bimetallic nanoparticles in phase contrast high resolution electron microscopy (HREM) images was developed. In this study, we discuss problems in applying HREM techniques to single metal (Pt and Au) and bimetallic (AuPd) nanoparticles of unknown shapes and random orientations. Errors arising from particle tilt and edge effects are discussed and analysis criteria are presented to reduce these errors in measuring the lattice parameters of nanoparticles. The accuracy of an individual particle lattice measurement is limited by an effective standard deviation which depends on the size of the individual nanoparticle. For example, the standard deviation for 20-30 A Pt or Au nanoparticles is about 1.5%. To increase the accuracy in determining the lattice spacings of nanoparticles, statistical methods have to be used to obtain the average lattice spacing of an ensemble of nanoparticles. We measured approximately 100 nanoparticles with sizes in the range of 20-30 A and found that the mean lattice spacing can be determined to within 0.2%. By applying Vegard's law to the AuPd bimetallic systems we successfully detected the presence of alloying. For 30 A nanoparticles, the estimated ultimate error in determining the composition of the AuPd alloy is about 3% provided that at least 100 particles are measured. Finally, the challenges in determining the presence of more than one alloy phases in bimetallic nanoparticle systems were also discussed.

  10. Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

    DOEpatents

    Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

    2016-01-26

    Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

  11. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

    Foster, M. S.; Hesson, J. C.; Shimotake, H.

    1969-01-01

    Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

  12. METALLIC AND HYBRID NANOSTRUCTURES: FUNDAMENTALS AND APPLICATIONS

    SciTech Connect

    Murph, S.

    2012-05-02

    This book chapter presents an overview of research conducted in our laboratory on preparation, optical and physico-chemical properties of metallic and nanohybrid materials. Metallic nanoparticles, particularly gold, silver, platinum or a combination of those are the main focus of this review manuscript. These metallic nanoparticles were further functionalized and used as templates for creation of complex and ordered nanomaterials with tailored and tunable structural, optical, catalytic and surface properties. Controlling the surface chemistry on/off metallic nanoparticles allows production of advanced nanoarchitectures. This includes coupled or encapsulated core-shell geometries, nano-peapods, solid or hollow, monometallic/bimetallic, hybrid nanoparticles. Rational assemblies of these nanostructures into one-, two- and tridimensional nano-architectures is described and analyzed. Their sensing, environmental and energy related applications are reviewed.

  13. Cyclic carbonate synthesis catalysed by bimetallic aluminium-salen complexes.

    PubMed

    Clegg, William; Harrington, Ross W; North, Michael; Pasquale, Riccardo

    2010-06-18

    The development of bimetallic aluminium-salen complexes [{Al(salen)}(2)O] as catalysts for the synthesis of cyclic carbonates (including the commercially important ethylene and propylene carbonates) from a wide range of terminal epoxides in the presence of tetrabutylammonium bromide as a cocatalyst is reported. The bimetallic structure of one complex was confirmed by X-ray crystallography. The bimetallic complexes displayed exceptionally high catalytic activity and in the presence of tetrabutylammonium bromide could catalyse cyclic carbonate synthesis at atmospheric pressure and room temperature. Catalyst-reuse experiments demonstrated that one bimetallic complex was stable for over 60 reactions, though the tetrabutylammonium bromide decomposed in situ by a retro-Menschutkin reaction to form tributylamine and had to be regularly replaced. The mild reaction conditions allowed a full analysis of the reaction kinetics to be carried out and this showed that the reaction was first order in aluminium complex concentration, first order in epoxide concentration, first order in carbon dioxide concentration (except when used in excess) and unexpectedly second order in tetrabutylammonium bromide concentration. Further kinetic experiments demonstrated that the tributylamine formed in situ was involved in the catalysis and that addition of butyl bromide to reconvert the tributylamine into tetrabutylammonium bromide resulted in inhibition of the reaction. The reaction kinetics also indicated that no kinetic resolution of racemic epoxides was possible with this class of catalysts, even when the catalyst was derived from a chiral salen ligand. However, it was shown that if enantiomerically pure styrene oxide was used as substrate, then enantiomerically pure styrene carbonate was formed. On the basis of the kinetic and other experimental data, a catalytic cycle that explains why the bimetallic complexes display such high catalytic activity has been developed.

  14. Preparation of Au-Pt nanostructures by combining top-down with bottom-up strategies and application in label-free electrochemical immunosensor for detection of NMP22.

    PubMed

    Jia, Hongying; Gao, Picheng; Ma, Hongmin; Wu, Dan; Du, Bin; Wei, Qin

    2015-02-01

    A novel label-free amperometric immunosensor for sensitive detection of nuclear matrix protein 22 (NMP22) was developed based on Au-Pt bimetallic nanostructures, which were prepared by combining top-down with bottom-up strategies. Nanoporous gold (NPG) was prepared by "top-down" dealloying of commercial Au/Ag alloy film. After deposition of NPG on an electrode, Pt nanoparticles (PtNPs) were further decorated on NPG by "bottom-up" electrodeposition. The prepared bimetallic nanostructures combine the merits of both NPG and PtNPs, and show a high electrocatalytic activity towards the reduction of H2O2. The label-free immunosensor was constructed by directly immobilizing antibody of NMP22 (anti-NMP22) on the surface of bimetallic nanostructures. The immunoreaction induced amperometric response could be detected and negatively correlated to the concentration of NMP22. Bimetallic nanostructure morphologies and detection conditions were investigated to obtain the best sensing performance. Under the optimal conditions, a linear range from 0.01ng/mL to 10ng/mL and a detection limit of 3.33pg/mL were obtained. The proposed immunosensor showed high sensitivity, good selectivity, stability, reproducibility, and regeneration for the detection of NMP22, and it was evaluated in urine samples, receiving satisfactory results.

  15. Nanowire networks and hollow nanospheres of Ag–Au bimetallic alloys at room temperature

    NASA Astrophysics Data System (ADS)

    Britto Hurtado, R.; Cortez-Valadez, M.; Arizpe-Chávez, H.; Flores-Lopez, N. S.; Álvarez, Ramón A. B.; Flores-Acosta, M.

    2017-03-01

    Due to their physicochemical properties, metallic nanoalloys have potential applications in biomedicine, electrocatalysis and electrochemical sensors, among many other fields. New alternative procedures have emerged in order to reduce production costs and the use of toxic substances. In this study we present a novel low-toxicity synthesis method for the fabrication of nanowire networks (NWNs) and Ag–Au hollow nanospheres. The synthesis process is performed at room temperature without any sophisticated equipment, such as special cameras or furnaces, etc. Transmission electron microscopy showed that the NWNs contain random alloys with a diameter of between 10–13 nm. The radius for the hollow nanospheres is approximately located between 70–130 nm. The absorption bands in the UV–vis spectrum associated with the surface plasmon in Ag–Au bimetallic nanoparticles are highlighted at 385 nm for the NWNs and 643 nm for the hollow nanospheres. The study was performed with low-toxicity substances, such as rongalite, ascorbic acid and sucrose, and showed high efficiency for the fabrication of these types of nanostructures, as well as good stability for long periods of time.

  16. Nanowire networks and hollow nanospheres of Ag-Au bimetallic alloys at room temperature.

    PubMed

    Hurtado, R Britto; Cortez-Valadez, M; Arizpe-Chávez, H; Flores-Lopez, N S; Álvarez, Ramón A B; Flores-Acosta, M

    2017-03-17

    Due to their physicochemical properties, metallic nanoalloys have potential applications in biomedicine, electrocatalysis and electrochemical sensors, among many other fields. New alternative procedures have emerged in order to reduce production costs and the use of toxic substances. In this study we present a novel low-toxicity synthesis method for the fabrication of nanowire networks (NWNs) and Ag-Au hollow nanospheres. The synthesis process is performed at room temperature without any sophisticated equipment, such as special cameras or furnaces, etc. Transmission electron microscopy showed that the NWNs contain random alloys with a diameter of between 10-13 nm. The radius for the hollow nanospheres is approximately located between 70-130 nm. The absorption bands in the UV-vis spectrum associated with the surface plasmon in Ag-Au bimetallic nanoparticles are highlighted at 385 nm for the NWNs and 643 nm for the hollow nanospheres. The study was performed with low-toxicity substances, such as rongalite, ascorbic acid and sucrose, and showed high efficiency for the fabrication of these types of nanostructures, as well as good stability for long periods of time.

  17. Enhanced and tunable optical quantum efficiencies from plasmon bandwidth engineering in bimetallic CoAg nanoparticles

    NASA Astrophysics Data System (ADS)

    Malasi, A.; Taz, H.; Ehrsam, M.; Goodwin, J.; Garcia, H.; Kalyanaraman, R.

    2016-10-01

    Plasmonic nanoparticles are amongst the most effective ways to resonantly couple optical energy into and out of nanometer sized volumes. However, controlling and/or tuning the transfer of this incident energy to the surrounding near and far field is one of the most interesting challenges in this area. Due to the dielectric properties of metallic silver (Ag), its nanoparticles have amongst the highest radiative quantum efficiencies (η), i.e., the ability to radiatively transfer the incident energy to the surrounding. Here we report the discovery that bimetallic nanoparticles of Ag made with immiscible and plasmonically weak Co metal can show comparable and/or even higher η values. The enhancement is a result of the narrowing of the plasmon bandwidth from these bimetal systems. The phenomenological explanation of this effect based on the dipolar approximation points to the reduction in radiative losses within the Ag nanoparticles when in contact with cobalt. This is also supported by a model of coupling between poor and good conductors based on the surface to volume ratio. This study presents a new type of bandwidth engineering, one based on using bimetal nanostructures, to tune and/or enhance the quality factor and quantum efficiency for near and far-field plasmonic applications.

  18. Nickel Cobaltite Nanostructures for Photoelectric and Catalytic Applications.

    PubMed

    Liu, Shaoxiong; Hu, Linfeng; Xu, Xiaojie; Al-Ghamdi, Ahmed A; Fang, Xiaosheng

    2015-09-09

    Bimetallic oxide nickel cobaltite (NiCo2 O4 ) shows extensive potential for innovative photoelectronic and energetic materials owing to their distinctive physical and chemical properties. In this review, representative fabrications and applications of NiCo2 O4 nanostructures are outlined for photoelectronic conversion, catalysis, and energy storage, aiming to promote the development of NiCo2 O4 nanomaterials in these fields through an analysis and comparison of their diverse nanostructures. Firstly, a brief introduction of the spinel structures, properties, and morphologies of NiCo2 O4 nanomaterials are presented. Then, the advanced progress of NiCo2 O4 nanomaterials for both photoelectronic conversion and energy fields is summarized including such examples as solar cells, electrocatalysis, and lithium ion batteries. Finally, further prospects and promising developments of NiCo2 O4 nanomaterials in these significant fields are proposed.

  19. Structural Characterization of Bimetallic Nanocrystal Electrocatalysts

    SciTech Connect

    Cullen, David A

    2016-01-01

    Late transition metal nanocrystals find applications in heterogeneous catalysis such as plasmon-enhanced catalysis and as electrode materials for fuel cells, a zero-emission and sustainable energy technology. Their commercial viability for automotive transportation has steadily increased in recent years, almost exclusively due to the discovery of more efficient bimetallic nanocatalysts for the oxygen reduction reaction (ORR) at the cathode. Despite improvements to catalyst design, achieving high activity while maintaining durability is essential to further enhance their performance for this and other important applications in catalysis. Electronic effects arising from the generation of metal-metal interfaces, from plasmonic metals, and from lattice distortions, can vastly improve sorption properties at catalytic surfaces, while increasing durability.[1] Multimetallic lattice-strained nanoparticles are thus an interesting opportunity for fundamental research.[2,3] A colloidal synthesis approach is demonstrated to produce AuPd alloy and Pd@Au core-shell nanoicosahedra as catalysts for electro-oxidations. The nanoparticles are characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and large solid angle energy dispersive X-ray spectroscopy (EDS) on an FEI Talos 4-detector STEM/EDS system. Figure 1 shows bright-field (BF) and high-angle annular dark-field (HAADF) ac-STEM images of the alloy and core-shell nanoicosahedra together with EDS line-scans and elemental maps. These structures are unique in that the presence of twin boundaries, alloying, and core-shell morphology could create highly strained surfaces and interfaces. The shell thickness of the core-shell structures observed in HAADF-STEM images is tuned by adjusting the ratio between metal precursors (Figure 2a-f) to produce shells ranging from a few to several monolayers. Specific activity was measured in ethanol electro-oxidation to examine the effect of shell thickness on

  20. Nanostructured photovoltaics

    NASA Astrophysics Data System (ADS)

    Fu, Lan; Tan, H. Hoe; Jagadish, Chennupati

    2013-01-01

    Energy and the environment are two of the most important global issues that we currently face. The development of clean and sustainable energy resources is essential to reduce greenhouse gas emission and meet our ever-increasing demand for energy. Over the last decade photovoltaics, as one of the leading technologies to meet these challenges, has seen a continuous increase in research, development and investment. Meanwhile, nanotechnology, which is considered to be the technology of the future, is gradually revolutionizing our everyday life through adaptation and incorporation into many traditional technologies, particularly energy-related technologies, such as photovoltaics. While the record for the highest efficiency is firmly held by multijunction III-V solar cells, there has never been a shortage of new research effort put into improving the efficiencies of all types of solar cells and making them more cost effective. In particular, there have been extensive and exciting developments in employing nanostructures; features with different low dimensionalities, such as quantum wells, nanowires, nanotubes, nanoparticles and quantum dots, have been incorporated into existing photovoltaic technologies to enhance their performance and/or reduce their cost. Investigations into light trapping using plasmonic nanostructures to effectively increase light absorption in various solar cells are also being rigorously pursued. In addition, nanotechnology provides researchers with great opportunities to explore the new ideas and physics offered by nanostructures to implement advanced solar cell concepts such as hot carrier, multi-exciton and intermediate band solar cells. This special issue of Journal of Physics D: Applied Physics contains selected papers on nanostructured photovoltaics written by researchers in their respective fields of expertise. These papers capture the current excitement, as well as addressing some open questions in the field, covering topics including the

  1. Nanosegregated bimetallic oxide anode catalyst for proton exchange membrane electrolyzer

    DOEpatents

    Danilovic, Nemanja; Kang, Yijin; Markovic, Nenad; Stamenkovic, Vojislav; Myers, Deborah J.; Subbaraman, Ram

    2016-08-23

    A surface segregated bimetallic composition of the formula Ru.sub.1-xIr.sub.x wherein 0.1.ltoreq.x.ltoreq.0.75, wherein a surface of the material has an Ir concentration that is greater than an Ir concentration of the material as a whole is provided. The surface segregated material may be produced by a method including heating a bimetallic composition of the formula Ru.sub.1-xIr.sub.x, wherein 0.1.ltoreq.x.ltoreq.0.75, at a first temperature in a reducing environment, and heating the composition at a second temperature in an oxidizing environment. The surface segregated material may be utilized in electrochemical devices.

  2. Bimetallic reactivity. On the use of oxadiazoles as binucleating ligands.

    PubMed

    Incarvito, C; Rheingold, A L; Qin, C J; Gavrilova, A L; Bosnich, B

    2001-03-12

    Two (1,3,4)-oxadiazole ligands have been prepared. In one case the oxadiazole ring is flanked by two o-aniline groups, and in the other case it is an extension of the first where the amines are condensed with 2-picolyl groups. A monometallic copper(II) complex of the former has been prepared, and its crystal structure was determined. A number of bimetallic copper(II), cobalt(II), and nickel(II) complexes of the di-deprotonated latter ligand were prepared and isolated. The crystal structure of the cobalt(II) complex bearing two acetate bridges is reported. The work demonstrates that the seldom-employed oxadiazole ring can be used effectively for generating bimetallic complexes.

  3. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    NASA Astrophysics Data System (ADS)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

  4. Extended X-ray absorption fine structure of bimetallic nanoparticles

    PubMed Central

    2011-01-01

    Summary Electronic and magnetic properties strongly depend on the structure of the material, especially on the crystal symmetry and chemical environment. In nanoparticles, the break of symmetry at the surface may yield different physical properties with respect to the corresponding bulk material. A useful tool to investigate the electronic structure, magnetic behaviour and local crystallographic structure is X-ray absorption spectroscopy. In this review, recent developments in the field of extended X-ray absorption fine structure measurements and in the analysis methods for structural investigations of bimetallic nanoparticles are highlighted. The standard analysis based on Fourier transforms is compared to the relatively new field of wavelet transforms that have the potential to outperform traditional analysis, especially in bimetallic alloys. As an example, the lattice expansion and inhomogeneous alloying found in FePt nanoparticles is presented, and this is discussed below in terms of the influence of employed density functional theory calculations on the magnetic properties. PMID:21977436

  5. Centrifugally cast bimetallic pipe for offshore corrosion resistant pipelines

    SciTech Connect

    Yoshitake, A.; Torigoe, T.

    1994-12-31

    Centrifugally cast bimetallic pipes and fittings have been developed for the use of offshore oil and gas production. The metallurgical properties, mechanical properties, and corrosion properties of centrifugal a cast bimetallic pipe with outside metal of API 5L X52 to X65 internally clad with alloy 825 and 625 are discussed. First, molten steel for outer pipe is introduced into a rotating metallic mold. During the solidification of the outer pipe (carbon steel), the temperature of the pipe inside is monitored. After the solidification of the outer pipe, and when a certain temperature is reached, then a corrosion resistant alloy such as Alloy 825 or 625 for inside layer is poured. By controlling the casting conditions and selecting suitable flux, sound metallurgical bonded bimetallic pipe is produced with a minimum mixing layer at the interface also keeping a homogeneous outside wall thickness along the pipe length. The weld joints of the pipe are also evaluated from the view points of weldability, mechanical strength, fracture toughness, and corrosion resistance properties. The welding method applied was basically TIG welding (GTAW). COD tests at {minus}10 C are applied to the welds to investigate fracture toughness of the weld joints. Huey test according to ASTM A262C is carried out on the root of the welds as the corrosion test. As a result, the weld joint using filler wire of alloy625 from root to cover pass has proved a very reliable method from the point of view of mechanical and corrosion resistance properties. These centrifugally cast bimetallic pipes and fittings have been widely used for riser pipes, template process lines, top side and subsea manifolds, and flow bends for christmas trees in the North Sea.

  6. Biosupported Bimetallic Pd Au Nanocatalysts for Dechlorination of Environmental Contaminants

    SciTech Connect

    De Corte, S.; Fitts, J.; Hennebel, T.; Sabbe, T.; Bliznuk, V.; Verschuere, S.; van der Lelie, D.; Verstraete, W.; Boon, N.

    2011-08-30

    Biologically produced monometallic palladium nanoparticles (bio-Pd) have been shown to catalyze the dehalogenation of environmental contaminants, but fail to efficiently catalyze the degradation of other important recalcitrant halogenated compounds. This study represents the first report of biologically produced bimetallic Pd/Au nanoparticle catalysts. The obtained catalysts were tested for the dechlorination of diclofenac and trichloroethylene. When aqueous bivalent Pd(II) and trivalent Au(III) ions were both added to concentrations of 50 mg L{sup -1} and reduced simultaneously by Shewanella oneidensis in the presence of H{sub 2}, the resulting cell-associated bimetallic nanoparticles (bio-Pd/Au) were able to dehalogenate 78% of the initially added diclofenac after 24 h; in comparison, no dehalogenation was observed using monometallic bio-Pd or bio-Au. Other catalyst-synthesis strategies did not show improved dehalogenation of TCE and diclofenac compared with bio-Pd. Synchrotron-based X-ray diffraction, (scanning) transmission electron microscopy and energy dispersive X-ray spectroscopy indicated that the simultaneous reduction of Pd and Au supported on cells of S. oneidensis resulted in the formation of a unique bimetallic crystalline structure. This study demonstrates that the catalytic activity and functionality of possibly environmentally more benign biosupported Pd-catalysts can be improved by coprecipitation with Au.

  7. Lightweight Beryllium Free Nanostructured Nanostructured Composites

    DTIC Science & Technology

    2007-11-02

    Plasma Processes, Inc. Lightweight Beryllium Free Nanostructured Composites SBIR Contract DASG60-02-P-41 Phase I Final Report 1/15/03 Submitted by...Report Type N/A Dates Covered (from... to) - Title and Subtitle Lightweight Beryllium Free Nanostructured Nanostructured Composites Contract

  8. PREPARATION OF NOVEL METALLIC AND BIMETALLIC CROSS-LINKED POLY (VINYL ALCOHOL) NANOCOMPOSITES UNDER MICROWAVE IRRADIATION

    EPA Science Inventory

    A facile method utilizing microwave irradiation is described that accomplishes the cross-linking reaction of PVA with metallic and bimetallic systems. Nanocomposites of PVA-cross-linked metallic systems such as Pt, Cu, and In and bimetallic systems such as Pt-In, Ag-Pt, Pt-Fe, Cu...

  9. NOVEL METALLIC AND BIMETALLIC CROSS-LINKED POLY (VINYL ALCOHOL) NANOCOMPOSITES PREPARED UNDER MICROWAVE IRRADIATION

    EPA Science Inventory

    A facile microwave irradiation approach that results in a cross-linking reaction of poly (vinyl alcohol) (PVA) with metallic and bimetallic systems is described. Nanocomposites of PVA cross-linked metallic systems such as Pt, Cu, and In and bimetallic systems such as Pt-In, Ag-P...

  10. DNA nanostructure meets nanofabrication.

    PubMed

    Zhang, Guomei; Surwade, Sumedh P; Zhou, Feng; Liu, Haitao

    2013-04-07

    Recent advances in DNA nanotechnology have made it possible to construct DNA nanostructures of almost arbitrary shapes with 2-3 nm of precision in their dimensions. These DNA nanostructures are ideal templates for bottom-up nanofabrication. This review highlights the challenges and recent advances in three areas that are directly related to DNA-based nanofabrication: (1) fabrication of large scale DNA nanostructures; (2) pattern transfer from DNA nanostructure to an inorganic substrate; and (3) directed assembly of DNA nanostructures.

  11. Formation of bimetallic nanoalloys by Au coating of size-selected Cu clusters

    NASA Astrophysics Data System (ADS)

    Yin, Feng; Wang, Zhi Wei; Palmer, Richard E.

    2012-10-01

    Bimetallic clusters display new characteristics that could not be obtained by varying either the size of pure metallic systems or the composition of bulk bimetals alone. Coating of pre-deposited clusters by vapour deposition is a typical synthesis process of bimetallic clusters. Here, we have demonstrated that hierarchical, gold cluster-decorated copper clusters as well as both heterogeneous and homogeneous Cu-Au bimetallic clusters (4.6 to 10.7 nm) can be prepared by coating pre-deposited, size-selected Cu5000 (4.6 ± 0.2 nm) with Au evaporation at various temperatures. These bimetallic clusters were analyzed by aberration-corrected scanning transmission electron microscopy and associated electron energy loss spectroscopy. The results indicate that the growth of bimetallic clusters is controlled by a competition between nucleation and diffusion of the coating Au atoms.

  12. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Mulvey, Robert E.; Blair, Victoria L.; Clegg, William; Kennedy, Alan R.; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC4) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C4 fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

  13. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran.

    PubMed

    Mulvey, Robert E; Blair, Victoria L; Clegg, William; Kennedy, Alan R; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC(4)) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C(4) fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

  14. Novel of core-shell AlOOH/Cu nanostructures: Synthesis, characterization, antimicrobial activity and in vitro toxicity in Neuro-2a cells

    NASA Astrophysics Data System (ADS)

    Bakina, O. V.; Fomenko, A. N.; Korovin, M. S.; Glazkova, E. A.; Svarovskaya, N. V.

    2016-08-01

    Core-shell micro/nanostructures were fabricated by the reaction of Al/Cu bimetallic nanoparticles with water. Al/Cu nanoparticles have been obtained using the method of simultaneous electrical explosion of a pair of the corresponding metal wires in an argon atmosphere. The nanoparticles are chemically active and interact with water at 60°C to form core-shell micro/nanostructures. The obtained products were characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy and dynamic light scattering and the nitrogen adsorption method. The antibacterial activity of the synthesized structures was investigated against E. coli and St. aureus. The toxic effect of these nanostructures against the Neuro-2a neuroblastoma cell line was investigated. AlOOH/Cu nanostructures are shown to inhibit cell proliferation. The AlOOH/Cu nanostructures are good candidates for medical applications.

  15. A density functional theory study of the adsorption of bimetallic Fe n Pt m clusters on defective graphene: structural, electronic, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Xu, Duo; Zhao, Jingxiang; Wang, Xuanzhang

    2013-04-01

    Recent studies have suggested that graphene can serve as an excellent support material for the synthesis of advanced metal nanoparticle-graphene electrocatalysts. Compared with single-metal systems, rational design of bimetallic nanostructures with various compositions can provide more attractive opportunities to enhance their functionalities because of the novel electronic and magnetic properties. In this study, we have studied the adsorption of a series of bimetallic Fe n Pt m clusters ( n + m ≤ 4) on defective graphene with monovacancy by performing density functional theory calculations. Particular attention is paid to addressing the structural stability and exploring the effects of Fe n Pt m clusters anchoring on the electronic and magnetic properties of defective graphene. The results reveal that all studied Fe n Pt m clusters can be stably adsorbed on defective graphene, with large binding energies ranging from 6.44 (for Fe2Pt2) to 7.94 eV (for Fe2Pt). Moreover, the functionalized defective graphenes exhibit semiconducting or half-metallic nature, which is dependent on the values of n and m. Meanwhile, most of decorated defective graphenes exhibit nonzero magnetic moments, contributed mainly by the adsorbed clusters. In addition, these composites of Fe n Pt m /graphenes possess high chemical reactivity toward O2. The elongation of the O-O bonds of the adsorbed O2 molecules indicates that they can be used as oxidative catalysts.

  16. A lightweight bimetallic actuator for spacecraft thermal control

    NASA Technical Reports Server (NTRS)

    Schilling, K. L.

    1971-01-01

    The design, development, and construction of two types of active thermal-control systems are described. These designs are based on the controlled angular deflections of spiral-wound bimetallic actuators. The use of these actuators and lightweight louvers results in a frictionless system that is low in weight yet simple in design and low in cost. Both designs exhibit high reliability, good performance repeatability, and do not require power from the spacecraft. Design philosophy and implementation, design tradeoffs, and materials selection are reviewed. The test program is described, and results are presented.

  17. Chemical- or Radiation-Assisted Selective Dealloying in Bimetallic Nanoclusters

    NASA Astrophysics Data System (ADS)

    Mattei, G.; Marchi, G. De; Maurizio, C.; Mazzoldi, P.; Sada, C.; Bello, V.; Battaglin, G.

    2003-02-01

    A selective dealloying in bimetallic nanoclusters prepared by ion implantation has been found upon thermal annealing in oxidizing atmosphere or irradiation with light ions. In the first process, the incoming oxygen interacts preferentially with copper promoting Cu2O formation, therefore extracting copper from the alloy. In the second process the irradiation with Ne ions promotes a preferential extraction of Au from the alloy, resulting in the formation of Au-enriched “satellite” nanoparticles around the original AuxCu1-x cluster.

  18. Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

    2015-06-01

    In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

  19. From First Principles Design to Realization of Bimetallic Catalysts for Ultrahigh Selectivity - Final Project Report

    SciTech Connect

    Richard M. Crooks

    2007-04-11

    (A) Synthesis, Characterization, and Fundamental Properties of Bimetallic DENs. AuAg alloy and core/shell bimetallic DENs were synthesized and characterized. Selective extraction was used as a structural characterization tool for these bimetallic nanoparticles. This is significant because there are few easily accessible methods for structure elucidation of bimetallic nanoparticles in this size regime. As a first step towards the synthesis of catalytically active, bimetallic heterogeneous materials we reported the incorporation of Au and Pd monometallic DENs and AuPd bimetallic DENs into amorphous titania networks. The compositional fidelity of the original DENs, and to some extent their size, is retained following dendrimer removal. Gas-phase catalytic activity for CO oxidation is higher for the bimetallic catalysts than for the corresponding Pd-only and Au-only monometallics. (B) Electrocatalysts based on dendrimer-encapsulated nanoparticles. Platinum dendrimer-encapsulated nanoparticles (DENs) were prepared within fourth-generation, hydroxyl-terminated, poly(amidoamine) dendrimers and immobilized on glassy carbon electrodes using an electrochemical immobilization strategy. X-ray photoelectron spectroscopy, electron microscopy, and electrochemical experiments confirm that the Pt DENs are about 1.4 nm in diameter and that they remain within the dendrimer following surface immobilization. The resulting Pt DEN films were electrocatalytically active for the oxygen reduction reaction (ORR). The films are also robust, surviving up to 50 consecutive cyclic voltammograms and sonication. Monometallic Pd DENs were also prepared and found to have little catalytic activity for the ORR. However, PtPd bimetallic DENs had catalytic activity nearly identical to that found for Pt-only DENs. This indicates an overall catalytic enhancement for the bimetallic electrocatalysts.

  20. Mechanical properties of bimetallic one-dimensional structures

    NASA Astrophysics Data System (ADS)

    Smelova, Ekaterina M.; Sitnikov, Ivan I.; Zelensky, Vladimir S.; Tsysar, Kseniya M.; Andreev, Valery G.; Vdovin, Vladimir A.; Saletsky, Alexander M.

    2016-12-01

    Mechanical properties of freestanding Au-Mn nanowires and Au-Mn nanowire on a Cu (110) substrate are studied with ab initio theoretical approach. The calculations were carried out using the software package Vienna Ab-initio Simulation Package (VASP), which is based on the density functional theory (DFT). It was shown that the breaking force (0.45nN) as well as the interatomic distance at a breaking point in bimetallic nanowire (3.0 Å) are higher than in one component Au wire (0.4 nN and 2.6Å respectively). Relative elongation of 15 % results in a fracture of bimetallic nanowire. We studied the mechanical response of the nanojunction in a form of three-atomic Au chain aligned vertically between two pyramidal gold electrodes and demonstrated that the breaking of nanocontact depends only the interaction between Au atoms in the chain and dependents slightly on the structure and properties of the atomic structure of the electrodes.

  1. Electronic and magnetic properties of bimetallic ytterbocene complexes: the impact of bridging ligand geometry.

    PubMed

    Carlson, Christin N; Veauthier, Jacqueline M; John, Kevin D; Morris, David E

    2008-01-01

    Bimetallic ytterbocene complexes with bridging N-heterocylic ligands have been studied extensively in recent years due to their potential applications ranging from molecular wires to single-molecule magnets. Herein, we review our recent results for a series of ytterbocene polypyridyl bimetallic complexes to highlight the versatility and tunability of these systems based on simple changes in bridging ligand geometry. Our work has involved structural, electrochemical, optical, and magnetic measurements with the goal of better understanding the electronic and magnetic communication between the two ytterbium metal centers in this new class of bimetallics.

  2. Physical and Numerical Analysis of Extrusion Process for Production of Bimetallic Tubes

    SciTech Connect

    Misiolek, W.Z.; Sikka, V.K.

    2006-08-10

    Bimetallic tubes are used for very specific applications where one of the two metals provides strength and the other provides specific properties such as aqueous corrosion and carburization, coking resistance, and special electrical and thermal properties. Bimetallic tubes have application in pulp and paper industry for heat-recovery boilers, in the chemical industry for ethylene production, and in the petrochemical industry for deep oil well explorations. Although bimetallic tubes have major applications in energy-intensive industry, they often are not used because of their cost and manufacturing sources in the United States. This project was intended to address both of these issues.

  3. Tuning the Composition of AuPt Bimetallic Nanoparticles for Antibacterial Application**

    PubMed Central

    Zhao, Yuyun; Ye, Chunjie; Liu, Wenwen; Chen, Rong; Jiang, Xingyu

    2014-01-01

    We show that bimetallic nanoparticles (NPs) of AuPt without any surface modification are potent antibiotic reagents, while pure Au NPs or pure Pt NPs display no antibiotic activities. The most potent antibacterial AuPt NPs happen to be the most effective catalysts for chemical transformations. The mechanism of antibiotic action includes the dissipation of membrane potential and the elevation of adenosine triphosphate (ATP) levels. These bimetallic NPs are unique in that they do not produce reactive oxygen species as most antibiotics do. Being non-toxic to human cells, these bimetallic noble NPs might open an entry to a new class of antibiotics. PMID:24828967

  4. Sustainable Strategy Utilizing Biomass: Visible-Light-Mediated Synthesis of γ-Valerolactone

    EPA Science Inventory

    A novel sustainable approach to valued γ-valerolactone is described that exploits visible light mediated conversion of biomass-derived levulinic acid using a bimetallic catalyst on graphitic carbon nitride, AgPd@g-C3N4.

  5. A sustainable approach to empower the bio-based future: upgrading of biomass via process intensification

    EPA Science Inventory

    An economically viable and environmentally benign continuous flow intensified process has been developed to demonstrate the ability to upgrade biomass into potential biofuels, solvents, and pharmaceutical feedstocks using a bimetallic AgPd@g-C3N4 catalyst.

  6. SERS activity studies of Ag/Au bimetallic films prepared by galvanic replacement.

    PubMed

    Wang, Chaonan; Fang, Jinghuai; Jin, Yonglong

    2012-10-01

    Ag films on Si substrates were fabricated by immersion plating, which served as sacrificial materials for preparation of Ag/Au bimetallic films by galvanic replacement method. SEM images displayed that the sacrificial Ag films presenting island morphology experienced interesting structural evolution process during galvanic replacement reaction, and nano-scaled holes were formed in the resultant bimetallic films. SERS measurements using crystal violet as an analyte showed that SERS intensities of bimetallic films were enhanced significantly compared with that of pure Ag films and related mechanisms were discussed. Immersion plating experiment carried out on Ag films on PEN substrates fabricated by photoinduced reduction method further confirmed that galvanic replacement is an easy method to fabricate Ag/Au bimetallic and a potential approach to improve the SERS performance of Ag films.

  7. Facile synthesis of Cu-Pd bimetallic multipods for application in cyclohexane oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Zhuo-Qun; Huang, Jianliu; Zhang, Lan; Sun, Mei; Wang, You-Cheng; Lin, Yue; Zeng, Jie

    2014-10-01

    The synergy between Cu and Pd makes Cu-Pd bimetallic nanocrystals interesting materials for investigation. The scarcity of shapes of Cu-Pd bimetallic nanocrystals motivated us to explore highly branched structures, which may promote a wide range of applications. In this communication, we report a facile synthesis of Cu-Pd bimetallic multipods (19.2 ± 1.2 nm), on branches of which some high-index facets were exposed. Modification of reaction parameters concerning capping agents and reductant led to the formation of other shapes, including sphere-like nanocrystals (SNCs). When loaded onto TiO2, the as-prepared Cu-Pd bimetallic multipods exhibited excellent catalytic activity for the oxidation of cyclohexane by hydrogen peroxide and higher selectivity towards cyclohexanone than monometallic catalysts and SNCs/TiO2.

  8. Chemistry of Bimetallic Linked Cyclopentadienyl Complexes: Progress Report, 1 December 1986 --30 November 1989

    DOE R&D Accomplishments Database

    Schrock, R. R.

    1989-01-01

    Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. (CBS)

  9. Bimetallic Nanoshells for Metal – Enhanced Fluorescence with Broad Band Fluorophores

    PubMed Central

    Zhang, Jian; Fu, Yi; Mahdavi, Farhad

    2012-01-01

    In this article, we reported the near-field interactions between the Ru(bpy)32+ complexes and plasmon resonances from the bimetallic nanoshells. The metallic nanoshells were fabricated on 20 nm silica spheres as cores by depositing 10 nm monometallic or bimetallic shells. There were approx. 15 Ru(bpy)32+ complexes in the silica core. The metal shells were constituted of silver or/and gold. The bimetallic shells could be generated in homogeneous or heterogeneous geometries. The homogeneous bimetallic shells contained 10 nm silver-gold alloys. The heterogeneous bimetallic shells contained successive 5 nm gold and 5 nm silver shells, or alternatively, 5 nm silver and 5 nm gold shells. Optical properties of metal nanoshells were studied on both the ensemble spectra and single nanoparticle imaging measurements. The heterogeneous bimetallic shells were found to have a large scale of metal-enhanced emission relative to the monometallic or homogeneous bimetallic shells. It is because the heterogeneous bimetallic shells may display split dual plasmon resonances which can interact with the excitation and emission bands of the Ru(bpy)32+ complexes in the silica cores leading to more efficient near-field interactions. The prediction can be demonstrated by the lifetimes. Therefore, it is suggested that both the compositions and geometries of the metal shells can influence the interactions with the fluorophores in the cores. This observation also offers us an opportunity for developing plasmon-based fluorescence metal nanoparticles as novel nanoparticle imaging agents which have high performances in fluorescence cell or tissue imaging. PMID:23230456

  10. Levelling the playing field: screening for synergistic effects in coalesced bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Tan, Rachel Lee Siew; Song, Xiaohui; Chen, Bo; Chong, Wen Han; Fang, Yin; Zhang, Hua; Wei, Jun; Chen, Hongyu

    2016-02-01

    Depending on the synthetic methods, bimetallic nanoparticles can have either core-shell, phase segregated, alloy, or partially coalesced structures, presenting different degrees of atomic mixing on their surface. Along with the variations of size and morphology, the structural differences make it difficult to compare the catalytic activity of bimetallic nanoparticles. In this article, we developed a facile screening method that can focus on the synergistic effects rather than structural differences. Prefabricated nanoparticles are mixed together to form linear aggregates and coalesced to form bimetallic junctions. Their hollow silica shells allow materials transport but prevent further aggregation. With a level playing field, this screening platform can identify the best bimetallic combination for a catalytic reaction, before optimizing the synthesis. This approach is more advantageous than the conventional approaches where structural difference may have dominant effects on the catalytic performance.Depending on the synthetic methods, bimetallic nanoparticles can have either core-shell, phase segregated, alloy, or partially coalesced structures, presenting different degrees of atomic mixing on their surface. Along with the variations of size and morphology, the structural differences make it difficult to compare the catalytic activity of bimetallic nanoparticles. In this article, we developed a facile screening method that can focus on the synergistic effects rather than structural differences. Prefabricated nanoparticles are mixed together to form linear aggregates and coalesced to form bimetallic junctions. Their hollow silica shells allow materials transport but prevent further aggregation. With a level playing field, this screening platform can identify the best bimetallic combination for a catalytic reaction, before optimizing the synthesis. This approach is more advantageous than the conventional approaches where structural difference may have dominant

  11. Gyroscopic behavior exhibited by the optical Kerr effect in bimetallic Au-Pt nanoparticles suspended in ethanol

    NASA Astrophysics Data System (ADS)

    Fernández-Valdés, D.; Torres-Torres, C.; Martínez-González, C. L.; Trejo-Valdez, M.; Hernández-Gómez, L. H.; Torres-Martínez, R.

    2016-07-01

    The modification in the third-order nonlinear optical response exhibited by rotating bimetallic Au-Pt nanoparticles in an ethanol solution was analyzed. The samples were prepared by a sol-gel processing route. The anisotropy associated to the elemental composition of the nanoparticles was confirmed by high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements. The size of the nanoparticles varies in the range from 9 to 13 nm, with an average size of 11 nm. Changes in the spatial orientation of the nanomaterials automatically generated a variation in their plasmonic response evaluated by UV-Vis spectroscopy. A two-wave mixing experiment was conducted to explore an induced birefringence at 532 nm wavelength with nanosecond pulses interacting with the samples. A strong optical Kerr effect was identified to be the main responsible effect for the third-order nonlinear optical phenomenon exhibited by the nanoparticles. It was estimated that the rotation of inhomogeneous nanostructures can provide a remarkable change in the participation of different surface plasmon resonances, if they correspond to multimetallic nanoparticles. Potential applications for developing low-dimensional gyroscopic systems can be contemplated.

  12. Lattice-matched bimetallic CuPd-graphene nanocatalysts for facile conversion of biomass-derived polyols to chemicals.

    PubMed

    Jin, Xin; Dang, Lianna; Lohrman, Jessica; Subramaniam, Bala; Ren, Shenqiang; Chaudhari, Raghunath V

    2013-02-26

    A bimetallic nanocatalyst with unique surface configuration displays extraordinary performance for converting biomass-derived polyols to chemicals, with potentially much broader applications in the design of novel catalysts for several reactions of industrial relevance. The synthesis of nanostructured metal catalysts containing a large population of active surface facets is critical to achieve high activity and selectivity in catalytic reactions. Here, we describe a new strategy for synthesizing copper-based nanocatalysts on reduced graphene oxide support in which the catalytically active {111} facet is achieved as the dominant surface by lattice-match engineering. This method yields highly active Cu-graphene catalysts (turnover frequency = 33-114 mol/g atom Cu/h) for converting biopolyols (glycerol, xylitol, and sorbitol) to value-added chemicals, such as lactic acid and other useful co-products consisting of diols and linear alcohols. Palladium incorporation in the Cu-graphene system in trace amounts results in a tandem synergistic system in which the hydrogen generated in situ from polyols is used for sequential hydrogenolysis of the feedstock itself. Furthermore, the Pd addition remarkably enhances the overall stability of the nanocatalysts. The insights gained from this synthetic methodology open new vistas for exploiting graphene-based supports to develop novel and improved metal-based catalysts for a variety of heterogeneous catalytic reactions.

  13. Preparation and characterization of dendrimer-templated Ag-Cu bimetallic nanoclusters.

    PubMed

    Li, Guoping; Luo, Yunjun

    2008-01-07

    Ag-Cu bimetallic nanoclusters with different shapes were prepared by a co-complexation method in the presence of PAMAM dendrimers. Small and evenly sized spherical Ag-Cu bimetallic nanoparticles were obtained with N2H4.H2O as the reducing agent, and long rod-shaped bimetallic nanoclusters were prepared with NaBH4 as the reducing agent. The mechanisms of formation of Ag-Cu bimetallic nanolusters with different shapes were discussed. The different shapes of the cluster were likely caused by the differences in the reduction rate of metal ions with NaBH4 and N2H4.H2O. Structure characterization by TEM, UV-vis spectra, EDX, and TGA showed that, in the presence of PAMAM dendrimers, Ag-Cu alloy bimetallic nanorods were obtained with NaBH4 reduction, and Ag-Cu bimetallic nanoparticles were prepared with N2H4.H2O as the reducing agent.

  14. Mapping thermal conductivity using bimetallic atomic force microscopy probes

    NASA Astrophysics Data System (ADS)

    Grover, Ranjan; McCarthy, Brendan; Sarid, Dror; Guven, Ibrahim

    2006-06-01

    We demonstrate a technique to measure local thermal conductivity of materials using an atomic force microscope equipped with a commercial silicon cantilever coated by a thin metal film. This bimaterial cantilever acts as a bimetallic strip that bends when heated by a focused laser beam. The bending is apparent as a topographic distortion, which varies with the amount of heat flowing from the cantilever's tip into the sample. By comparing the surface topographies of the sample, as measured with heated and unheated cantilevers, the local thermal conductivity of the tip-sample contact area can be determined. Experimental results with this system are presented and found to be in good agreement with a finite element model.

  15. STEM-EDX tomography of bimetallic nanoparticles: A methodological investigation.

    PubMed

    Slater, Thomas J A; Janssen, Arne; Camargo, Pedro H C; Burke, M Grace; Zaluzec, Nestor J; Haigh, Sarah J

    2016-03-01

    This paper presents an investigation of the limitations and optimisation of energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope, focussing on application of the technique to characterising the 3D elemental distribution of bimetallic AgAu nanoparticles. The detector collection efficiency when using a standard tomography holder is characterised using a tomographic data set from a single nanoparticle and compared to a standard low background double tilt holder. Optical depth profiling is used to investigate the angles and origin of detector shadowing as a function of specimen field of view. A novel time-varied acquisition scheme is described to compensate for variations in the intensity of spectrum images at each sample tilt. Finally, the ability of EDX spectrum images to satisfy the projection requirement for nanoparticle samples is discussed, with consideration of the effect of absorption and shadowing variations.

  16. A theory of adhesion at a bimetallic interface - Overlap effects.

    NASA Technical Reports Server (NTRS)

    Ferrante, J.; Smith, J. R.

    1973-01-01

    A preliminary calculation of the chemical bonding adhesive interaction between metal surfaces is provided. In this first theory the Hohenberg and Kohn formalism is used to give the bimetallic adhesive binding energy versus separation. The close-packed planes of Al, Mg, and Zn are considered. The effect of simple overlap of the metal-vacuum distributions is determined. The importance of registry between contact surfaces is ascertained. A minimum in the binding energy curve is exhibited for all combinations. The theoretical predictions agree with trends in bond strengths taken from available experimental data. An insight into the mechanisms involved in metallic transfer is given. The relationship between adhesive energies, cohesive energies, and surface energies is discussed.

  17. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

  18. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    SciTech Connect

    Schoeb, Ann M.

    1997-10-17

    The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO2 catalysts for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO2, Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.

  19. Bulk-Forming Simulation of Bimetallic Watchcase Components

    NASA Astrophysics Data System (ADS)

    Kong, T. F.; Chan, L. C.

    2014-10-01

    This article presents a study of the effects of process parameters in bulk-forming bimetallic watchcase components using finite-element (FE) simulation. This study aimed to determine the suitable forming temperature T and ram speed S for attaining the complete die filling of bimetals. A complicated watchcase component made of 3-mm-thick AISI 316L stainless steel (SS316L) and 6-mm-thick 6063 aluminum alloy (AA6063) was used as the example. The processes were simulated with T of 400°C, 500°C, 600°C, 700°C, 800°C, and 900°C and S of 20 mm/s, 40 mm/s, and 60 mm/s. Although the AA6063 was not heated in the beginning, it flowed faster than the SS316L during the process, and hence, the incomplete die filling was found mainly in the SS316L region. To avoid the incomplete die filling and strengthen the intermetallic bond between two dissimilar metals, the T of 900°C was suggested. The S of 40 mm/s was recommended also because this could save much forming energy and prevent the damage of tools. The experimental verification was carried out under process conditions that were employed in the simulations. An infrared thermal imaging camera and a 300-ton mechanical press were used to monitor the T and testify the bulk-forming operation, respectively. The data acquired from the experiments, on average, agreed strongly with those predicted by the simulations. On the basis of the results in this study, engineers can gain a better understanding of bulk-forming bimetallic components and be able to determine the T and S efficiently for similar processes.

  20. Nanostructured composite reinforced material

    DOEpatents

    Seals, Roland D [Oak Ridge, TN; Ripley, Edward B [Knoxville, TN; Ludtka, Gerard M [Oak Ridge, TN

    2012-07-31

    A family of materials wherein nanostructures and/or nanotubes are incorporated into a multi-component material arrangement, such as a metallic or ceramic alloy or composite/aggregate, producing a new material or metallic/ceramic alloy. The new material has significantly increased strength, up to several thousands of times normal and perhaps substantially more, as well as significantly decreased weight. The new materials may be manufactured into a component where the nanostructure or nanostructure reinforcement is incorporated into the bulk and/or matrix material, or as a coating where the nanostructure or nanostructure reinforcement is incorporated into the coating or surface of a "normal" substrate material. The nanostructures are incorporated into the material structure either randomly or aligned, within grains, or along or across grain boundaries.

  1. Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

    NASA Astrophysics Data System (ADS)

    Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

    2016-11-01

    Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d5/2 shifted to higher positions while that of Au 4f7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity. For the bimetallic catalysts, a disproportional increase of turnover frequency (TOF) was observed with increasing Au content due to the enhanced cationization of Pd particles. Moreover, the dechlorination of 2,4-DCP over the supported monometallic and bimetallic catalysts proceeded via both the stepwise and concerted pathway, and the concerted pathway became predominant with Au decoration amount in the catalyst.

  2. Synthesis of branched metal nanostructures with controlled architecture and composition

    NASA Astrophysics Data System (ADS)

    Ortiz, Nancy

    On account of their small size, metal nanoparticles are proven to be outstanding catalysts for numerous chemical transformations and represent promising platforms for applications in the fields of electronics, chemical sensing, medicine, and beyond. Many properties of metal nanoparticles are size-dependent and can be further manipulated through their shape and architecture (e.g., spherical vs. branched). Achieving morphology control of nanoparticles through solution-based techniques has proven challenging due to limited knowledge of morphology development in nanosyntheses. To overcome these complications, a systematic examination of the local ligand environment of metal precursors on nanostructure formation was undertaken to evaluate its contribution to nanoparticle nucleation rate and subsequent growth processes. Specifically, this thesis will provide evidence from ex situ studies---Transmission Electron Microscopy (TEM) and UV-visible spectroscopy (UV-Vis)---that support the hypothesis that strongly coordinated ligands delay burst-like nucleation to generate spherical metal nanoparticles and ligands with intermediate binding affinity regulate the gradual reduction of metal precursors to promote aggregated assembly of nanodendrites. These ex situ studies were coupled with a new in situ perspective, providing detailed understanding of metal precursor transformation, its direct relation to nanoparticle morphology development, and the ligand influence towards the formation of structurally complex metal nanostructures, using in situ synchrotron X-ray Diffraction (XRD) and Ultra Small-Angle X-ray Scattering (USAXS). The principles extracted from the study of monometallic nanostructure formation were also found to be generally applicable to the synthesis of bimetallic nanostructures, e.g., Pd-Pt architectures, with either core-shell or alloyed structures that were readily achieved by ligand selection. These outcomes provide a direct connection between fundamental

  3. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry.

    PubMed

    Durham, Jessica L; Poyraz, Altug S; Takeuchi, Esther S; Marschilok, Amy C; Takeuchi, Kenneth J

    2016-09-20

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multifunctionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cations can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multimechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM'O) or phosphorus oxides (MM'PO) where M = Ag and M' = V or Fe. One discharge process can be described as reduction-displacement where Ag(+) is reduced to Ag(0) and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity, determining the

  4. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

    SciTech Connect

    Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; Marschilok, Amy C.; Takeuchi, Kenneth J.

    2016-08-26

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and mass of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag+ is reduced to Ag0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional

  5. Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry

    DOE PAGES

    Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.; ...

    2016-08-26

    Electric energy storage devices such as batteries are complex systems comprised of a variety of materials with each playing separate yet interactive roles, complicated by length scale interactions occurring from the molecular to the mesoscale. Thus, addressing specific battery issues such as functional capacity requires a comprehensive perspective initiating with atomic level concepts. For example, the electroactive materials which contribute to the functional capacity in a battery comprise approximately 30% or less of the total device mass. Thus, the design and implementation of multifunctional materials can conceptually reduce or eliminate the contribution of passive materials to the size and massmore » of the final system. Material multi-functionality can be achieved through appropriate material design on the atomic level resulting in bimetallic electroactive materials where one metal cation forms mesoscale conductive networks upon discharge while the other metal cation can contribute to atomic level structure and net functional secondary capacity, a device level issue. Specifically, this Account provides insight into the multi-mechanism electrochemical redox processes of bimetallic cathode materials based on transition metal oxides (MM’O) or phosphorous oxides (MM’PO) where M = Ag and M’ = V or Fe. One discharge process can be described as reduction-displacement where Ag+ is reduced to Ag0 and displaced from the parent structure. This reduction-displacement reaction in silver-containing bimetallic electrodes allows for the in-situ formation of a conductive network, enhancing the electrochemical performance of the electrode and reducing or eliminating the need for conductive additives. A second discharge process occurs through the reduction of the second transition metal, V or Fe, where the oxidation state of the metal center is reduced and lithium cations are inserted into the structure. As both metal centers contribute to the functional capacity

  6. A novel and greener approach for shape controlled synthesis of gold and gold-silver core shell nanostructure and their application in optical coatings.

    PubMed

    Sinha, Tanur; Ahmaruzzaman, M

    2015-06-15

    Green and facile synthetic methods have gained marvellous fame for the production of polyhedral, anisotropic and spherical gold, and gold-silver bimetallic nanostructures. The useful pivotal characteristics of a green procedure are the usage of environment benign solvent medium, reducing and stabilising agents, and shorter reaction time. We describe here a novel, and greener method for the production of gold and gold-silver core shell nanostructures using aqueous fish scales extract of the Labeo rohita. The effect of various reaction parameters, such as temperature and concentration for the synthesis of the nanostructures were studied. Results indicated that triangular and decahedron gold nanostructures were formed at a lower temperature (40°C) and concentration (10%). While, icosahedral and spherical gold nanostructures were produced at a comparatively higher temperature (100°C) and concentration (40%). The study also revealed that the core-shell bimetallic nanostructures with different morphologies (spherical and oval-shape) were formed at different ratios of chloroaurate and silver nitrate solution. Thus, the present study indicated a simple shape controlled synthesis of gold and gold silver core-shell nanostructures. The synthesised gold nanotriangles were coated over the glass substrate and found to be highly efficient in absorbing infra-red radiations for potential architectural applications. Therefore, the study demonstrated the facile usage of gold nanotriangles for optical coatings. The present strategy depicted the dual functional ability of the fish scale extract as reducing and stabilising agents. This strategy also eliminates the usage of hazardous chemicals, toxic solvents and harsh reducing and stabilizing agents.

  7. A novel and greener approach for shape controlled synthesis of gold and gold-silver core shell nanostructure and their application in optical coatings

    NASA Astrophysics Data System (ADS)

    Sinha, Tanur; Ahmaruzzaman, M.

    2015-06-01

    Green and facile synthetic methods have gained marvellous fame for the production of polyhedral, anisotropic and spherical gold, and gold-silver bimetallic nanostructures. The useful pivotal characteristics of a green procedure are the usage of environment benign solvent medium, reducing and stabilising agents, and shorter reaction time. We describe here a novel, and greener method for the production of gold and gold-silver core shell nanostructures using aqueous fish scales extract of the Labeo rohita. The effect of various reaction parameters, such as temperature and concentration for the synthesis of the nanostructures were studied. Results indicated that triangular and decahedron gold nanostructures were formed at a lower temperature (40 °C) and concentration (10%). While, icosahedral and spherical gold nanostructures were produced at a comparatively higher temperature (100 °C) and concentration (40%). The study also revealed that the core-shell bimetallic nanostructures with different morphologies (spherical and oval-shape) were formed at different ratios of chloroaurate and silver nitrate solution. Thus, the present study indicated a simple shape controlled synthesis of gold and gold silver core-shell nanostructures. The synthesised gold nanotriangles were coated over the glass substrate and found to be highly efficient in absorbing infra-red radiations for potential architectural applications. Therefore, the study demonstrated the facile usage of gold nanotriangles for optical coatings. The present strategy depicted the dual functional ability of the fish scale extract as reducing and stabilising agents. This strategy also eliminates the usage of hazardous chemicals, toxic solvents and harsh reducing and stabilizing agents.

  8. Magnetic properties of bimetallic Au/Co nanoparticles prepared by thermal laser treatment

    NASA Astrophysics Data System (ADS)

    Sosunov, A. V.; Spivak, L. V.

    2016-07-01

    The irradiation of metallic films by a nanosecond pulsed laser leads to a self-assembly of nanoparticle arrays. This method has been used to prepare bimetallic Au/Co nanoparticles on a SiO2 substrate. The microstructure and morphology of the bimetallic nanoparticles have been investigated using scanning electron microscopy and transmission electron microscopy. It has been shown that the bimetallic nanoparticles have a hemispherical shape with a single-crystal structure and an average size of ~50 nm. The magnetic properties of these nanoparticles have been examined using a vibrating-sample magnetometer in the transverse and longitudinal directions. It has been found that the direction of the magnetization of the bimetallic nanoparticles lies in the plane of the substrate, and the coercive forces in the transverse and longitudinal directions differ by 25%. The use of the vibrating-sample magnetometer method makes it possible to investigate the differences in the magnetic saturations and the coercive forces of an array of bimetallic nanoparticles on a large surface area. The performed investigations have demonstrated that the anisotropic nanomagnetic materials with the desired magnetic orientation can be easily and quickly prepared by means of thermal laser treatment.

  9. Effect of Synthesis Techniques on Crystallization and Optical Properties of Ag-Cu Bimetallic Nanoparticles

    NASA Astrophysics Data System (ADS)

    Xiong, Ziye; Qin, Fen; Huang, Po-Shun; Nettleship, Ian; Lee, Jung-Kun

    2016-04-01

    Silver (Ag)-copper (Cu) bimetallic nanoparticles (NPs) were synthesized by the reduction of silver nitrate and copper (II) acetate monohydrate using ethylene glycol in a microwave (MW) heating system with controlled reaction times ranging from 5 min to 30 min. The molar ratio Ag/Cu was varied from 1:1 to 1:3. The effect of reaction conditions on the bimetallic NPs structures and compositions were characterized by x-ray photoelectron spectroscopy, x-ray diffraction and transmission electron microscopy. The average particle size was approximately 150 nm. The surface plasmon resonance (SPR) of Ag-Cu bimetallic NPs was investigated by monitoring the SPR band peak behavior via UV/Vis spectrophotometry. The resonance peak positions and peak widths varied due to the different structures of the bimetallic NPs created under the synthesis conditions. In the MW heating method, the reduction of Cu was increased and Cu was inhomogeneously deposited over the Ag cores. As the composition of Cu becoming higher in the Ag-Cu bimetallic NPs, the absorption between 400 nm to 600 nm was greatly enhanced.

  10. Hydrodechlorination of chlorobenzene over polymer-stabilized palladium-platinum bimetallic colloidal nanocatalysts.

    PubMed

    Liu, Manhong; Wang, Chao; Yu, William W

    2010-11-01

    Poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized Pd, Pt, Pd-Pt nanocatalysts were prepared and characterized by transmission electron microscopy (TEM). Hydrogenation of chlorobenzene was carried out over these colloidal nanocatalysts under ambient conditions. The catalytic properties for the hydrogenation of chlorobenzene depended on the composition of the bimetallic nanocatalysts. The conversion of chlorobenzene over PVP-Pd (83.64%) was higher than that of PVP-Pt (66.67%), which indicated that the activity of Pd was higher than that of Pt. In 10 hrs. the conversions of all the bimetallic nanocatalysts were higher than that of PVP-Pt (66.67%) monometallic nanocatalysts, and the maximum conversion of chlorobenzene (95.34%) was achieved using PVP-Pd/Pt = 1/1 catalytic system, which was much higher than that of the physical mixture of monometallic nanocatalysts (PVP-Pd and PVP-Pt) at the same Pd/Pt ratio as the PVP-Pd/Pt bimetallic nanocatalysts used. The selectivity to benzene and cyclohexane of the bimetallic nanocatalysts (with < or = 40 mol% Pt) was similar to that of PVP-Pd monometallic nanocatalysts, and nearly approximately 100% selectivity to benzene could be obtained, the selectivity to cyclohexane increased slowly with increasing of platinum content in bimetallic nanocatalysts.

  11. Synthesis and characteristics of Ag/Pt bimetallic nanocomposites by arc-discharge solution plasma processing.

    PubMed

    Pootawang, Panuphong; Saito, Nagahiro; Takai, Osamu; Lee, Sang-Yul

    2012-10-05

    Arc discharge in solution, generated by applying a high voltage of unipolar pulsed dc to electrodes of Ag and Pt, was used as a method to form Ag/Pt bimetallic nanocomposites via electrode erosion by the effects of the electric arc at the cathode (Ag rod) and the sputtering at the anode (Pt rod). Ag/Pt bimetallic nanocomposites were formed as colloidal particles dispersed in solution via the reduction of hydrogen radicals generated during discharge without the addition of chemical precursor or reducing agent. At a discharge time of 30 s, the fine bimetallic nanoparticles with a mean particle size of approximately 5 nm were observed by transmission electron microscopy (TEM). With increasing discharge time, the bimetallic nanoparticle size tended to increase by forming an agglomeration. The presence of the relatively small amount of Pt dispersed in the Ag matrix could be observed by the analytical mapping mode of energy-dispersive x-ray spectroscopy and high-resolution TEM. This demonstrated that the synthesized particle was in the form of a nanocomposite. No contamination of other chemical substances was detected by x-ray photoelectron spectroscopy. Hence, solution plasma could be a clean and simple process to effectively synthesize Ag/Pt bimetallic nanocomposites and it is expected to be widely applicable in the preparation of several types of nanoparticle.

  12. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-07-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and OI) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles.

  13. Nanostructured Protective Coatings

    DTIC Science & Technology

    2006-01-01

    potential superior wear resistance properties. The Nanostructured Protective Coatings (NPC) program was designed to establish a collaborative team of...understanding of PVD parameters, depositing coatings on practical substrates such as the Ti6Al4V used for turbine blades , and developing a versatile...Nanostructured Protective Coatings (NPC) program was designed to establish a collaborative team of three entities (Pennsylvania State University

  14. Size-depressed critical temperatures for the order-disorder transition of FePt, CoPt, FePb, Cu2S, and ZnS nanostructures

    NASA Astrophysics Data System (ADS)

    Jiang, R.; Zhou, Z. F.; Yang, X. X.; Guo, N. G.; Qi, W. H.; Sun, C. Q.

    2013-01-01

    The size dependency of the critical temperature (TC) for the order-disorder phase transitions of both the bimetallic and the chalcogenide nanoclusters is shown to follow the rule of bond order-length-strength correlation. The loss of the cohesive energy of the undercoordinated atoms in the surface skin dictates the structural stability. Theoretical reproduction of the size TC trends of FePt, CoPt, FePb, Cu2S, and ZnS nanostructures not only confirms our expectations without involving the concepts of surface energy or entropy used for continuum bulk materials but also provides guideline for engineering nanostructured alloys or compounds.

  15. Regeneration of sulfur-fouled bimetallic Pd-based catalysts.

    PubMed

    Chaplin, Brian P; Shapley, John R; Werth, Charles J

    2007-08-01

    Pd-based catalysts provide efficient and selective reduction of several drinking water contaminants, but their long-term application requires effective treatments for catalyst regeneration following fouling by constituents in natural waters. This studytested alumina-supported Pd-Cu and Pd-In bimetallic catalysts for nitrate reduction with H2 after sulfide fouling and oxidative regeneration procedures. Both catalysts were severely deactivated after treatment with microM levels of sulfide. Regeneration was attempted with dissolved oxygen, hydrogen peroxide, sodium hypochlorite, and heated air. Only sodium hypochlorite and heated air were effective regenerants, specifically restoring nitrate reduction rates for a Pd-In/gamma-Al2O3 catalyst from 20% to between 39 and 60% of original levels. Results from ICP-MS revealed that sodium hypochlorite caused dissolution of Cu from the Pd-Cu catalyst but that the Pd-In catalyst was chemically stable over a range of sulfide fouling and oxidative regenerative conditions. Analysis byXPS indicated that PdS and In2S3 complexes form during sulfide fouling, where sulfur is present as S2-, and that regeneration with sodium hypochlorite converts a portion of the S2- to S6+, with a corresponding increase in reduction rates. These results indicate that Pd-In catalysts show exceptional promise for being robust under fouling and regeneration conditions that may occur when treating natural waters.

  16. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    SciTech Connect

    Chunshan, Song; Kirby, S.; Schmidt, E.

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  17. Salt flux synthesis of single and bimetallic carbide nanowires

    NASA Astrophysics Data System (ADS)

    Leonard, Brian M.; Waetzig, Gregory R.; Clouser, Dale A.; Schmuecker, Samantha M.; Harris, Daniel P.; Stacy, John M.; Duffee, Kyle D.; Wan, Cheng

    2016-07-01

    Metal carbide compounds have a broad range of interesting properties and are some of the hardest and highest melting point compounds known. However, their high melting points force very high reaction temperatures and thus limit the formation of high surface area nanomaterials. To avoid the extreme synthesis temperatures commonly associated with these materials, a new salt flux technique has been employed to reduce reaction temperatures and form these materials in the nanometer regime. Additionally, the use of multiwall carbon nanotubes as a reactant further reduces the diffusion distance and provides a template for the final carbide materials. The metal carbide compounds produced through this low temperature salt flux technique maintain the nanowire morphology of the carbon nanotubes but increase in size to ˜15-20 nm diameter due to the incorporation of metal in the carbon lattice. These nano-carbides not only have nanowire like shape but also have much higher surface areas than traditionally prepared metal carbides. Finally, bimetallic carbides with composition control can be produced with this method by simply using two metal precursors in the reaction. This method provides the ability to produce nano sized metal carbide materials with size, morphology, and composition control and will allow for these compounds to be synthesized and studied in a whole new size and temperature regime.

  18. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, Nilesh

    1996-10-17

    Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory information, the literature review, general conclusions, and four appendices. An additional four chapters and one appendix have been processed separately for inclusion on the data base.

  19. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    DOE PAGES

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

  20. Vibrational spectroscopic studies of adsorbates on bimetallic surfaces. Doctoral thesis

    SciTech Connect

    Kuhn, W.K.

    1992-12-01

    In this work, well-defined bimetallic surfaces have been studied using carbon monoxide adsorption in conjunction with infrared reflection absorption spectroscopy (IRAS). These studies have indicated that for CO adsorbed on Cu overlayers, the bond between the CO and the Cu adatoms is comprised of both pi-back-donation and polarization interaction components. The sum of the contributions from these effects determines the observed bond strength with the observed CO stretching frequency being determined by the relative contributions of the components. In addition, it was determined that IR spectra of adsorbed CO show a remarkable sensitivity to surface structure. Three-dimensional Cu clusters, well-ordered two dimensional Cu islands and isolated Cu atoms are distinctively characterized by their CO IR peaks. In addition, both disorder-order and order-order transitions are observed for the metal overlayers on the single crystal metal substrates. It was also observed that localized segregation and ordering of mixed Co and S overlayers on a Mo(110) substrate occurs upon annealing.

  1. Stellated Ag-Pt bimetallic nanoparticles: An effective platform for catalytic activity tuning

    PubMed Central

    Liu, Hui; Ye, Feng; Yao, Qiaofeng; Cao, Hongbin; Xie, Jianping; Lee, Jim Yang; Yang, Jun

    2014-01-01

    The usefulness of Pt-based nanomaterials for catalysis can be greatly enhanced by coupling morphology engineering to the strategic presence of a second or even third metal. Here we demonstrate the design and preparation of stellated Ag-Pt bimetallic nanoparticles where significant activity difference between the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) may be realized by relegating Ag to the core or by hollowing out the core. In particular the stellated Pt surface, with an abundance of steps, edges, corner atoms, and {111} facets, is highly effective for the ORR but is ineffective for MOR. MOR activity is only observed in the presence of a Ag core through electronic coupling to the stellated Pt shell. The bimetallic Ag-Pt stellates therefore demonstrate the feasibility of tuning a Pt surface for two very different structure sensitive catalytic reactions. Stellated bimetallics may therefore be an effective platform for highly tunable catalyst designs. PMID:24495979

  2. Synthesis of supported bimetallic nanoparticles with controlled size and composition distributions for active site elucidation

    SciTech Connect

    Hakim, Sikander H.; Sener, Canan; Alba Rubio, Ana C.; Gostanian, Thomas M.; O'neill, Brandon J; Ribeiro, Fabio H.; Miller, Jeffrey T.; Dumesic, James A

    2015-08-01

    Elucidation of active sites in supported bimetallic catalysts is complicated by the high level of dispersity in the nanoparticle size and composition that is inherent in conventional methods of catalyst preparation. We present a synthesis strategy that leads to highly dispersed, bimetallic nanoparticles with uniform particle size and composition by means of controlled surface reactions. We demonstrate the synthesis of three systems, RhMo, PtMo, and RhRe, consisting of a highly reducible metal with an oxophilic promoter. These catalysts are characterized by FTIR, CO chemisorption, STEM/EDS, TPR, and XAS analysis. The catalytic properties of these bimetallic nanoparticles were probed for the selective CO hydrogenolysis of (hydroxymethyl)tetrahydropyran to produce 1,6 hexanediol. Based on the characterization results and reactivity trends, the active sites in the hydrogenolysis reaction are identified to be small ensembles of the more noble metal (Rh, Pt) adjacent to highly reduced moieties of the more oxophilic metal (Mo, Re).

  3. Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

    PubMed Central

    Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

    2016-01-01

    Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications. PMID:27471193

  4. Preparation of Pt/Rh bimetallic colloidal particles in polymer solutions using borohydride-reduction.

    PubMed

    Harada, Masafumi; Einaga, Hisahiro

    2007-04-15

    Colloidal dispersions of Pt/Rh bimetallic particles have been synthesized by the reduction of Pt(IV)/Rh(III) ionic solutions by using borohydride-reduction in the presence of poly(N-vinyl-2-pyrrolidone). The size and the structure of the synthesized particles have been examined by transmission electron micrograph (TEM) and extended X-ray absorption fine structure (EXAFS). We have succeeded in producing the bimetallic Pt/Rh particles with an average diameter of 2.8 nm in polymer solutions by the stepwise addition of sodium borohydride aqueous solution. The distribution of different metallic species in a particle tended to be "cluster-in-cluster" structure, in contrast to the bimetallic particle with an average diameter of 1.4 nm synthesized by alcohol-reduction which have a core-shell structure.

  5. EXAFS and XANES structural characterization of bimetallic AuPd vapor derived catalysts

    NASA Astrophysics Data System (ADS)

    Balerna, A.; Evangelisti, C.; Schiavi, E.; Vitulli, G.; Bertinetti, L.; Martra, G.; Mobilio, S.

    2013-04-01

    Using an innovative procedure known as metal vapor synthesis (MVS) to prepare bimetallic catalysts, starting from Au and Pd vapors, [AuPd] co-evaporated and [Au][Pd] separately evaporated bimetallic catalysts were achieved. After being tested, the catalytic activity and selectivity of the [AuPd] catalyst turned out to be higher than the [Au][Pd] ones. Using EXAFS spectroscopy it was shown that, in the [AuPd] samples, small bimetallic AuPd nanoparticles were present, having an Au rich core surrounded by an AuPd alloyed shell while in the [Au][Pd] sample there was the presence of monometallic Au and Pd nanoparticles showing some alloying only in the boundary regions. The EXAFS results were also qualitatively confirmed by the XANES spectra.

  6. General trend for adsorbate-induced segregation of subsurface metal atoms in bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Menning, Carl A.; Chen, Jingguang G.

    2009-05-01

    It is well known that the unique chemical properties of transition metal alloys depend on the configuration of metal atoms of the bimetallic surfaces. Using density functional theory calculations, the thermodynamic potential for segregation of an admetal from the subsurface to surface configuration is shown to correlate linearly with the difference in occupied d-band center, Δɛd, between these two configurations for a wide range of bimetallic systems. The thermodynamic potential for segregation is also shown to increase with the Pauling electronegativity for several adsorbates, including atomic H, O, C, N, S, and Se. A generalized equation is provided to predict the stable surface configuration for the bimetallic systems with different adsorbates.

  7. Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

    NASA Astrophysics Data System (ADS)

    Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

    2016-07-01

    Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications.

  8. Description of the performances of a thermo-mechanical energy harvester using bimetallic beams

    NASA Astrophysics Data System (ADS)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2016-06-01

    Many recent researches have been focused on the development of thermal energy harvesters using thermo-mechanical or thermo-electrical coupling phenomena associated to a first-order thermodynamic transition. In the case of the bimetallic strip heat engine, the exploitation of the thermo-mechanical instability of bimetallic membranes placed in a thermal gradient enables to convert heat into kinetic energy. This paper is a contribution to the modeling and the comprehension of these heat engines. By restraining the study to the simply-supported bimetallic beams and using a Ritz approximation of the beam shape, this paper aims to give an analytical solution to the first mode of the composite beams and then to evaluate the efficiency of the harvesters exploiting these kinds of instability.

  9. Design and performance benchmark of various architectures of a piezoelectric bimetallic strip heat engine

    NASA Astrophysics Data System (ADS)

    Boughaleb, J.; Arnaud, A.; Monfray, S.; Cottinet, P. J.; Quenard, S.; Boeuf, F.; Guyomar, D.; Skotnicki, T.

    2016-06-01

    This paper deals with an investigation of a thermal energy harvester based on the coupling of a piezoelectric membrane and a bimetallic strip heat engine. The general working principle of the device consists of a double conversion mechanism: the thermal energy is first converted into mechanical energy by means of a bimetallic strip, then the mechanical energy is converted into electricity with a piezoelectric membrane. This paper deals with the study and optimization of the harvester's design. First, the piezoelectric membrane configuration is studied to find the most efficient way to convert mechanical energy into electricity. A benchmark of various piezoelectric materials is then presented to point out the most efficient materials. Finally, our study focuses on the bimetallic strip's properties: the effect of its dimensions of its thermal hysteresis on the harvester's performances are studied and compared. Thanks to these different steps, we were able to point out the best configuration to convert efficiently thermal heat flux into electricity.

  10. Direct decomposition of methane over SBA-15 supported Ni, Co and Fe based bimetallic catalysts

    NASA Astrophysics Data System (ADS)

    Pudukudy, Manoj; Yaakob, Zahira; Akmal, Zubair Shamsul

    2015-03-01

    Thermocatalytic decomposition of methane is an alternative route for the production of COx-free hydrogen and carbon nanomaterials. In this work, a set of novel Ni, Co and Fe based bimetallic catalysts supported over mesoporous SBA-15 was synthesized by a facile wet impregnation route, characterized for their structural, textural and reduction properties and were successfully used for the methane decomposition. The fine dispersion of metal oxide particles on the surface of SBA-15, without affecting its mesoporous texture was clearly shown in the low angle X-ray diffraction patterns and the transmission electron microscopy (TEM) images. The nitrogen sorption analysis showed the reduced specific surface area and pore volume of SBA-15, after metal loading due to the partial filling of hexagonal mesopores by metal species. The results of methane decomposition experiments indicated that all of the bimetallic catalysts were highly active and stable for the reaction at 700 °C even after 300 min of time on stream (TOS). However, a maximum hydrogen yield of ∼56% was observed for the NiCo/SBA-15 catalyst within 30 min of TOS. A high catalytic stability was shown by the CoFe/SBA-15 catalyst with 51% of hydrogen yield during the course of reaction. The catalytic stability of the bimetallic catalysts was attributed to the formation of bimetallic alloys. Moreover, the deposited carbons were found to be in the form of a new set of hollow multi-walled nanotubes with open tips, indicating a base growth mechanism, which confirm the selectivity of SBA-15 supported bimetallic catalysts for the formation of open tip carbon nanotubes. The Raman spectroscopic and thermogravimetric analysis of the deposited carbon nanotubes over the bimetallic catalysts indicated their higher graphitization degree and oxidation stability.

  11. A theoretical approach for estimation of ultimate size of bimetallic nanocomposites synthesized in microemulsion systems

    NASA Astrophysics Data System (ADS)

    Salabat, Alireza; Saydi, Hassan

    2012-12-01

    In this research a new idea for prediction of ultimate sizes of bimetallic nanocomposites synthesized in water-in-oil microemulsion system is proposed. In this method, by modifying Tabor Winterton approximation equation, an effective Hamaker constant was introduced. This effective Hamaker constant was applied in the van der Waals attractive interaction energy. The obtained effective van der Waals interaction energy was used as attractive contribution in the total interaction energy. The modified interaction energy was applied successfully to predict some bimetallic nanoparticles, at different mass fraction, synthesized in microemulsion system of dioctyl sodium sulfosuccinate (AOT)/isooctane.

  12. INTERACTION OF SULPHUR WITH BIMETALLIC SURFACES: EFFECTS OF STRUCTURAL, ELECTRONIC AND CHEMICAL PROPERTIES.

    SciTech Connect

    RODRIGUEZ,J.A.; HRBEK,J.

    2001-10-04

    In recent years, several new interesting phenomena have been discovered when studying the interaction of sulphur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulphur can induce dramatic changes in the morphology of bimetallic surfaces. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond affect the reactivity of the bonded metals toward sulphur. This can be a very important issue to consider when trying to minimize the negative effects of sulphur poisoning or dealing with the design of desulfurization catalysts.

  13. Sonochemical preparation of bimetallic Co/Cu nanoparticles in aqueous solution

    SciTech Connect

    Jia Yaoshun; Niu Helin; Wu Mingzai; Ning Min; Zhu Hongfei; Chen Qianwang . E-mail: cqw@ustc.edu.cn

    2005-09-01

    Co/Cu bimetallic nanocrystallites, with average diameter of 50 nm, were prepared by a sonochemical method in the hydrazine solution of copper chloride and cobalt chloride. Cobalt was face-centered cubic phase when synthesized and remained fcc phase throughout the annealing process. X-ray diffractometer (XRD), transmission electron microscope (TEM), differential scanning calorimetry (DSC), vibrating sample magnetometry (VSM), inductively coupled plasma-atomic emission spectrometer (ICP-AES) measurements were carried out to investigate their structural and magnetic properties. It was found that the magnetic properties of bimetallic nanocrystallites were close to that of the sputtered alloys.

  14. (Plasmonic Metal Core)/(Semiconductor Shell) Nanostructures

    NASA Astrophysics Data System (ADS)

    Fang, Caihong

    shape is maintained throughout the sulfidation process, with the edge length being increased gradually. TiO2 is one of the most important semiconductors that are employed in light-harvesting applications. It has been extensively studied for a variety of applications by virtue of its low toxicity, biological compatibility, chemical and thermal stability, resistance to photocorrosion, and relative abundance. However, the photocatalytic activity of TiO2 is limited to the UV region because of its wide band gap, which limits its applications in light harvesting. Although (Au core)/(TiO2 shell) nanostructures can improve the photocatalytic activities of TiO2 in visible light, it has only been demonstrated in a few experiments and has been limited with Au nanospheres. Compared with Au nanospheres, Au nanorods offer more attractive plasmonic features, including stronger electric field enhancements and synthetically tunable longitudinal plasmon wavelengths over the visible to near-infrared region. The coating of Au nanorod therefore can largely improve light harvesting capability of TiO2. In this thesis, I developed a facile and versatile method for the preparation of (Au nanocrystal core)/(TiO2 shell) nanostructures by using a Ti(III) compound as the titania precursor. By employing Au nanorods with different sizes and varying the shell thickness, the plasmonic bands of the core/shell nanostructures can be tailored. TiO2 can also be grown on other monometallic and bimetallic Pd, Pt, Au nanocrystals. As a proof-of-concept application, (Au nanorod core)/(TiO2 shell) nanostructures were utilized in dye-sensitized solar cells to function as a scattering layer. The resultant solar cells exhibited higher power conversion efficiencies with a thinner thickness compared to the traditional TiO 2 solar cells. In addition, I also examined the property of plasmon-enhanced reactive oxygen species generation. Moreover, the TiO2 shell with a high refractive index can efficiently couple with the

  15. Nanoporous bimetallic Pt-Au alloy nanocomposites with superior catalytic activity towards electro-oxidation of methanol and formic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Zhonghua; Wang, Yan; Wang, Xiaoguang

    2011-04-01

    We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al75Pt15Au10 precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and energy dispersive X-ray (EDX) analysis. The Al75Pt15Au10 precursor is composed of a single-phase Al2(Au,Pt) intermetallic compound, and can be fully dealloyed in a 20 wt.% NaOH or 5 wt.% HCl aqueous solution. The dealloying leads to the formation of the nanoporous Pt60Au40 nanocomposites (np-Pt60Au40 NCs) with an fcc structure. The morphology, size and crystal orientation of grains in the precursor can be conserved in the resultant nanoporous alloy. The np-Pt60Au40 NCs consist of two zones with distinct ligament/channel sizes and compositions. The formation mechanism of these np-Pt60Au40 NCs can be rationalized based upon surface diffusion of more noble elements and spinodal decomposition during dealloying. Electrochemical measurements demonstrate that the np-Pt60Au40 NCs show superior catalytic activity towards the electro-oxidation of methanol and formic acid in the acid media compared to the commercial JM-Pt/C catalyst. This material can find potential applications in catalysis related areas, such as direct methanol or formic acidfuelcells. Our findings demonstrate that dealloying is an effective and simple strategy to realize the alloying of immiscible systems under mild conditions, and to fabricate novel nanostructures with superior performance.We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al75Pt15Au10 precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron

  16. Nanoporous bimetallic Pt-Au alloy nanocomposites with superior catalytic activity towards electro-oxidation of methanol and formic acid.

    PubMed

    Zhang, Zhonghua; Wang, Yan; Wang, Xiaoguang

    2011-04-01

    We present a facile route to fabricate novel nanoporous bimetallic Pt-Au alloy nanocomposites by dealloying a rapidly solidified Al(75)Pt(15)Au(10) precursor under free corrosion conditions. The microstructure of the precursor and the as-dealloyed sample was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and energy dispersive X-ray (EDX) analysis. The Al(75)Pt(15)Au(10) precursor is composed of a single-phase Al(2)(Au,Pt) intermetallic compound, and can be fully dealloyed in a 20 wt.% NaOH or 5 wt.% HCl aqueous solution. The dealloying leads to the formation of the nanoporous Pt(60)Au(40) nanocomposites (np-Pt(60)Au(40) NCs) with an fcc structure. The morphology, size and crystal orientation of grains in the precursor can be conserved in the resultant nanoporous alloy. The np-Pt(60)Au(40) NCs consist of two zones with distinct ligament/channel sizes and compositions. The formation mechanism of these np-Pt(60)Au(40) NCs can be rationalized based upon surface diffusion of more noble elements and spinodal decomposition during dealloying. Electrochemical measurements demonstrate that the np-Pt(60)Au(40) NCs show superior catalytic activity towards the electro-oxidation of methanol and formic acid in the acid media compared to the commercial JM-Pt/C catalyst. This material can find potential applications in catalysis related areas, such as direct methanol or formic acid fuel cells. Our findings demonstrate that dealloying is an effective and simple strategy to realize the alloying of immiscible systems under mild conditions, and to fabricate novel nanostructures with superior performance.

  17. Structure and properties of bimetallic titanium and vanadium oxide clusters.

    PubMed

    Helmich, Benjamin; Sierka, Marek; Döbler, Jens; Sauer, Joachim

    2014-05-14

    By employing a genetic algorithm together with density functional theory (B3LYP), we investigate the most stable minimum structures of several bimetallic titanium and vanadium oxide clusters that contain four metal atoms. The following compositions are studied: VnTin-4O10(-) (n = 1-4), (TiO2)VOn(-) (n = 1-4), and (TiO2)VOn(+) (n = 1-3). Apart from (TiO2)3VO(-), vanadium oxo groups are always part of the most stable minimum structures when vanadium is present. Anti-ferromagnetic coupling lowers the energy substantially if spin centers are located at neighbored metal atoms rather than at distant oxygen radical sites. Vanadium-rich or oxygen-poor compositions prefer symmetric adamantane-like cage structures, some of which have already been proposed in a previous study. In contrast, vanadium-poor and oxygen-rich compositions show versatile structural motifs that cannot be intuitively derived from the symmetric cage motif. Particularly, for Ti4O10(-) there are several non-symmetric and distorted cages that have an up to 68 kJ mol(-1) lower energy than the symmetric adamantane-like cage structure. Nevertheless, for the adamantane-like cage the simulated infra-red spectrum (within the harmonic approximation) agrees best with the experimental vibrational spectrum. The oxidative power of the (TiO2)3VO3(-) and (TiO2)3VO2(+) clusters as measured by the energy of removing 1/2 O2 (297 and 227 kJ mol(-1), respectively) is less than that of the pure vanadium oxide clusters (V2O5)VO3(-) and (V2O5)VO2(+) (283 and 165 kJ mol(-1), respectively).

  18. Development of clad boiler tubes extruded from bimetallic centrifugal castings

    SciTech Connect

    Sponseller, D.L.; Timmons, G.A.; Bakker, W.T.

    1995-12-31

    Wrought tubes of T-11 steel, externally clad with SS310, have been produced by a new method. The alloys were united directly from the molten state by centrifugal casting. In the optimum process, temperatures are controlled to prevent meltback of the SS310 outer layer by the higher-melting T-11 stream. Hollow extrusion billets were prepared from the heavy-walled cast bimetallic tubes and successfully hot extruded (at a ratio of 13.4) to 3.3-inch OD x 2.5-inch ID tubes, and (at a ratio of 37.6) to 2-inch OD x 1.5-inch ID tubes. In all, ten castings were produced, and 12 billets were extruded to tubes. For the most part, thicknesses of the cladding and tube wall are rather uniform around the circumference and from end to end of the tubes. Hardness and tensile Properties of annealed 2-inch tubes are uniform from end to 6nd of a tube, and between tubes, and readily conform to ASTM A 213; tubes satisfy the flattening and flaring requirements of ASTM A 450. The cladding is metallurgically bonded to the base metal, as revealed by metallography, and by two tests developed for this study: a bond hear-strength test and a twist test. In the latter test, rings 0.125 inch in thickness are slotted and severely twisted with a special tool. In tubes made by the optimum process, minute fissures that form adjacent to some of the pressure points during twist testing just 2.7 percent of the bond-line length. Cost estimates OCCUPY for commercial production of 2-inch tubes via the centrifugal casting route suggest that such tubes should be considerably less expensive than conventionally clad tubes (extruded from composite billets assembled from heavy-walled wrought tubes).

  19. Development of clad boiler tubes extruded from bimetallic centrifugal castings

    NASA Astrophysics Data System (ADS)

    Sponseller, D. L.; Timmons, G. A.; Bakker, W. T.

    1998-04-01

    Wrought tubes of T-11 steel, externally clad with SS310, have been produced by a new method (U.S. Patent 5,558,150). The alloys were united directly from the molten state by centrifugal casting. In the optimum process, temperatures were controlled to prevent meltback of the SS310 outer layer by the higher melting T-11 stream. Hollow extrusion billets were prepared from the heavy-walled cast bimetallic tubes and successfully hot extruded (at a ratio of 13.4) to 84-mm (3.3 in.) OD X 64-mm (2.5-in.) ID tubes, and (at a ratio of 37.6) to 51-mm (2-in.) OD X 38-mm (1.5-in.) ID tubes. In all, 10 castings were produced, and 12 billets were extruded to tubes. For the most part, thicknesses of the cladding and of the tube wall are rather uniform around the circumference and from end to end of the tubes. Hardness and tensile properties of annealed 51-mm (2-in.) tubes are uniform from end to end of a tube, and between tubes, and readily conform to ASTM A 213; tubes satisfy the flattening and flaring requirements of ASTM A 450. The cladding is metallurgically bonded to the base metal, as revealed by metallography, and by two tests developed for this study: a bond shear strength test and a twist test. In the latter test, rings 3.1 mm (0.125 in.) in thickness are slotted and severely twisted with a special tool. In tubes made by the optimum process, minute fissures that form adjacent to some of the pressure points during twist testing occupy just 3 % of the bond-line length. Cost estimates for commercial production of 51-mm (2-in.) tubes via the centrifugal casting route suggest that such tubes should be considerably less expensive than conventionally clad tubes (extruded from composite billets assembled from heavy-walled wrought tubes).

  20. Measuring Strong Nanostructures

    SciTech Connect

    Andy Minor

    2008-10-16

    Andy Minor of Berkeley Lab's National Center for Electron Microscopy explains measuring stress and strain on nanostructures with the In Situ Microscope. More information: http://newscenter.lbl.gov/press-relea...

  1. Measuring Strong Nanostructures

    ScienceCinema

    Andy Minor

    2016-07-12

    Andy Minor of Berkeley Lab's National Center for Electron Microscopy explains measuring stress and strain on nanostructures with the In Situ Microscope. More information: http://newscenter.lbl.gov/press-relea...

  2. Nanostructured Carbon Coatings

    DTIC Science & Technology

    2000-01-01

    carbon coatings and explores a very broad range of potentially important carbon nanostructures that may be used in future technologies. A new method ...for the synthesis of nanostructured carbon coatings on the surface of SiC and other metal carbides is described. This method is accomplished through the...With the fall in cost of fullerene powders, this method may become important in the future as a method to produce nanocrystalline diamond free of metal

  3. Architectures for Nanostructured Batteries

    NASA Astrophysics Data System (ADS)

    Rubloff, Gary

    2013-03-01

    Heterogeneous nanostructures offer profound opportunities for advancement in electrochemical energy storage, particularly with regard to power. However, their design and integration must balance ion transport, electron transport, and stability under charge/discharge cycling, involving fundamental physical, chemical and electrochemical mechanisms at nano length scales and across disparate time scales. In our group and in our DOE Energy Frontier Research Center (www.efrc.umd.edu) we have investigated single nanostructures and regular nanostructure arrays as batteries, electrochemical capacitors, and electrostatic capacitors to understand limiting mechanisms, using a variety of synthesis and characterization strategies. Primary lithiation pathways in heterogeneous nanostructures have been observed to include surface, interface, and both isotropic and anisotropic diffusion, depending on materials. Integrating current collection layers at the nano scale with active ion storage layers enhances power and can improve stability during cycling. For densely packed nanostructures as required for storage applications, we investigate both ``regular'' and ``random'' architectures consistent with transport requirements for spatial connectivity. Such configurations raise further important questions at the meso scale, such as dynamic ion and electron transport in narrow and tortuous channels, and the role of defect structures and their evolution during charge cycling. Supported as part of the Nanostructures for Electrical Energy Storage, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DESC0001160

  4. ELECTRONIC AND CHEMICAL PROPERTIES OF PD IN BIMETALLIC SYSTEMS: HOW MUCH DO WE KNOW ABOUT HETERONUCLEAR METAL-METAL BONDING?

    SciTech Connect

    RODRIGUEZ,J.A.

    2001-09-27

    The experimental and theoretical studies described above illustrate the complex nature of the heteronuclear metal-metal bond. In many cases, bimetallic bonding induces a significant redistribution of charge around the bonded metals. This redistribution of charge is usually linked to the strength of the bimetallic bond, affects the position of the core and valence levels of the metals, and can determine the chemical reactivity of the system under study. New concepts are emerging [22,23,34,36] and eventually the coupling of experiment and theory can be useful for designing more efficient bimetallic catalysts [98,106,107].

  5. Modeling of coalescence, agglomeration, and phase segregation in microgravity processing of bimetallic composite materials

    NASA Technical Reports Server (NTRS)

    Davis, Robert H.

    1992-01-01

    The overall objective of this research is to develop models to predict drop-size-distribution evolutions due to droplet collisions and coalescence during processing within the miscibility gap of bimetallic liquid-phase-miscibility-gap materials. The individual and collective action of gravitational and nongravitational mechanisms on the relative motion and coalescence of drops are considered.

  6. Optical properties of multilayer bimetallic films obtained by laser deposition of colloidal particles

    NASA Astrophysics Data System (ADS)

    Antipov, A.; Arakelian, S.; Vartanyan, T.; Gerke, M.; Istratov, A.; Kutrovskaya, S.; Kucherik, A.; Osipov, A.

    2016-11-01

    The optical properties of multilayer bimetallic films composed of silver and gold nanoparticles have been investigated. The dependence of the transmission spectra of the films on their morphology is demonstrated. A finite-difference time-domain (FDTD) simulation has confirmed that there is a dependence of the transmission spectra on the average distance between particles and the number of deposited layers.

  7. Green synthesis of Fe0 and bimetallic Fe0 for oxidative catalysis and reduction applications

    EPA Science Inventory

    A single-step green approach to the synthesis of nanoscale zero valent iron (nZVI) and nanoscale bimetallic (Fe0/Pd) particles using tea (Camellia sinensis) polyphenols is described. The expedient reaction between polyphenols and ferric chloride (FeCl3) occurs within a minute at ...

  8. Chemistry of bimetallic linked cyclopentadienyl complexes: Progress report, 1 December 1986--30 November 1989

    SciTech Connect

    Schrock, R.R.

    1986-12-01

    Research continued on the chemistry and preparation of bimetallic cyclopentadienyl complexes containing up to two tungsten or one tungsten and a cobalt, rhodium, or ruthenium. The general method for preparation and analysis of polyenes is also discussed. 7 figs., 2 tabs. (CBS)

  9. A Systematic Investigation of p-Nitrophenol Reduction by Bimetallic Dendrimer Encapsulated Nanoparticles

    PubMed Central

    2013-01-01

    We demonstrate that the reduction of p-nitrophenol to p-aminophenol by NaBH4 is catalyzed by both monometallic and bimetallic nanoparticles (NPs). We also demonstrate a straightforward and precise method for the synthesis of bimetallic nanoparticles using poly(amido)amine dendrimers. The resulting dendrimer encapsulated nanoparticles (DENs) are monodisperse, and the size distribution does not vary with different elemental combinations. Random alloys of Pt/Cu, Pd/Cu, Pd/Au, Pt/Au, and Au/Cu DENs were synthesized and evaluated as catalysts for p-nitrophenol reduction. These combinations are chosen in order to selectively tune the binding energy of the p-nitrophenol adsorbate to the nanoparticle surface. Following the Brønsted–Evans–Polanyi (BEP) relation, we show that the binding energy can reasonably predict the reaction rates of p-nitrophenol reduction. We demonstrate that the measured reaction rate constants of the bimetallic DENs is not always a simple average of the properties of the constituent metals. In particular, DENs containing metals with similar lattice constants produce a binding energy close to the average of the two constituents, whereas DENs containing metals with a lattice mismatch show a bimodal distribution of binding energies. Overall, in this work we present a uniform method for synthesizing pure and bimetallic DENs and demonstrate that their catalytic properties are dependent on the adsorbate’s binding energy. PMID:23616909

  10. A Systematic Investigation of p-Nitrophenol Reduction by Bimetallic Dendrimer Encapsulated Nanoparticles.

    PubMed

    Pozun, Zachary D; Rodenbusch, Stacia E; Keller, Emily; Tran, Kelly; Tang, Wenjie; Stevenson, Keith J; Henkelman, Graeme

    2013-04-18

    We demonstrate that the reduction of p-nitrophenol to p-aminophenol by NaBH4 is catalyzed by both monometallic and bimetallic nanoparticles (NPs). We also demonstrate a straightforward and precise method for the synthesis of bimetallic nanoparticles using poly(amido)amine dendrimers. The resulting dendrimer encapsulated nanoparticles (DENs) are monodisperse, and the size distribution does not vary with different elemental combinations. Random alloys of Pt/Cu, Pd/Cu, Pd/Au, Pt/Au, and Au/Cu DENs were synthesized and evaluated as catalysts for p-nitrophenol reduction. These combinations are chosen in order to selectively tune the binding energy of the p-nitrophenol adsorbate to the nanoparticle surface. Following the Brønsted-Evans-Polanyi (BEP) relation, we show that the binding energy can reasonably predict the reaction rates of p-nitrophenol reduction. We demonstrate that the measured reaction rate constants of the bimetallic DENs is not always a simple average of the properties of the constituent metals. In particular, DENs containing metals with similar lattice constants produce a binding energy close to the average of the two constituents, whereas DENs containing metals with a lattice mismatch show a bimodal distribution of binding energies. Overall, in this work we present a uniform method for synthesizing pure and bimetallic DENs and demonstrate that their catalytic properties are dependent on the adsorbate's binding energy.

  11. VAPOR PHASE MERCURY SORPTION BY ORGANIC SULFIDE MODIFIED BIMETALLIC IRON-COPPER NANOPARTICLE AGGREGATES

    EPA Science Inventory

    Novel organic sulfide modified bimetallic iron-copper nanoparticle aggregate sorbent materials have been synthesized for removing elemental mercury from vapor streams at elevated temperatures (120-140 °C). Silane based (disulfide silane and tetrasulfide silane) and alkyl sulfide ...

  12. Manufacturing Systems Demonstration: Bimetallic Friction STIR Joining of AA6061 and High Hardness Steel

    DTIC Science & Technology

    2013-05-31

    DESCRIPTION OF FRICTION STIR PROCESSES ................................................... 2 D. DEVELOPMENT OF BIMETALLIC ( ALUMINUM - STEEL ) FRICTION STIR...to successfully join AA6061 aluminum alloy and High Hardness Armor (HHA) steel using the friction stir process (FSP). Metallographic analysis...32262: Detail Specification, Armor Plate Aluminum Alloy, Unweldable Applique 6061 2 MIL-DTL-46100E: Armor Plate, Steel , Wrought, High-Hardness

  13. Borylation of propargylic substrates by bimetallic catalysis. Synthesis of allenyl, propargylic, and butadienyl Bpin derivatives.

    PubMed

    Zhao, Tony S N; Yang, Yuzhu; Lessing, Timo; Szabó, Kálmán J

    2014-05-28

    Bimetallic Pd/Cu and Pd/Ag catalytic systems were used for borylation of propargylic alcohol derivatives. The substrate scope includes even terminal alkynes. The reactions proceed stererospecifically with formal SN2' pathways to give allenyl boronates. Opening of propargyl epoxides leads to 1,2-diborylated butadienes probably via en allenylboronate intermediate.

  14. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    DOE PAGES

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; ...

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

  15. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    SciTech Connect

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; Stach, Eric A.; Senanayake, Sanjaya D.; Chen, Donna A.; Monnier, John R.; Weidner, John W.

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratio of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.

  16. Density and Shape Effects in the Acoustic Propulsion of Bimetallic Nanorod Motors.

    PubMed

    Ahmed, Suzanne; Wang, Wei; Bai, Lanjun; Gentekos, Dillon T; Hoyos, Mauricio; Mallouk, Thomas E

    2016-04-26

    Bimetallic nanorods are propelled without chemical fuels in megahertz (MHz) acoustic fields, and exhibit similar behaviors to single-metal rods, including autonomous axial propulsion and organization into spinning chains. Shape asymmetry determines the direction of axial movement of bimetallic rods when there is a small difference in density between the two metals. Movement toward the concave end of these rods is inconsistent with a scattering mechanism that we proposed earlier for acoustic propulsion, but is consistent with an acoustic streaming model developed more recently by Nadal and Lauga ( Phys. Fluids 2014 , 26 , 082001 ). Longer rods were slower at constant power, and their speed was proportional to the square of the power density, in agreement with the acoustic streaming model. The streaming model was further supported by a correlation between the disassembly of spinning chains of rods and a sharp decrease in the axial speed of autonomously moving motors within the levitation plane of the cylindrical acoustic cell. However, with bimetallic rods containing metals of different densities, a consistent polarity of motion was observed with the lighter metal end leading. Speed comparisons between single-metal rods of different densities showed that those of lower density are propelled faster. So far, these density effects are not explained in the streaming model. The directionality of bimetallic rods in acoustic fields is intriguing and offers some new possibilities for designing motors in which shape, material, and chemical asymmetry might be combined for enhanced functionality.

  17. Non-precious bimetallic catalysts for selective dehydrogenation of an organic chemical hydride system.

    PubMed

    Al-ShaikhAli, Anaam H; Jedidi, Abdesslem; Cavallo, Luigi; Takanabe, Kazuhiro

    2015-08-21

    Methylcyclohexane (MCH)-toluene (TOL) chemical hydride cycles as hydrogen carrier systems are successful with the selective dehydrogenation of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  18. Recent progress in the structure control of Pd–Ru bimetallic nanomaterials

    PubMed Central

    Wu, Dongshuang; Kusada, Kohei; Kitagawa, Hiroshi

    2016-01-01

    Abstract Pd and Ru are two key elements of the platinum-group metals that are invaluable to areas such as catalysis and energy storage/transfer. To maximize the potential of the Pd and Ru elements, significant effort has been devoted to synthesizing Pd–Ru bimetallic materials. However, most of the reports dealing with this subject describe phase-separated structures such as near-surface alloys and physical mixtures of monometallic nanoparticles (NPs). Pd–Ru alloys with homogenous structure and arbitrary metallic ratio are highly desired for basic scientific research and commercial material design. In the past several years, with the development of nanoscience, Pd–Ru bimetallic alloys with different architectures including heterostructure, core-shell structure and solid-solution alloy were successfully synthesized. In particular, we have now reached the stage of being able to obtain Pd–Ru solid-solution alloy NPs over the whole composition range. These Pd–Ru bimetallic alloys are better catalysts than their parent metal NPs in many catalytic reactions, because the electronic structures of Pd and Ru are modified by alloying. In this review, we describe the recent development in the structure control of Pd–Ru bimetallic nanomaterials. Aiming for a better understanding of the synthesis strategies, some fundamental details including fabrication methods and formation mechanisms are discussed. We stress that the modification of electronic structure, originating from different nanoscale geometry and chemical composition, profoundly affects material properties. Finally, we discuss open issues in this field. PMID:27877905

  19. Photoluminescent AuCu bimetallic nanoclusters as pH sensors and catalysts.

    PubMed

    Chen, Po-Cheng; Ma, Jia-Ying; Chen, Li-Yi; Lin, Guan-Lin; Shih, Chung-Chien; Lin, Tai-Yuan; Chang, Huan-Tsung

    2014-04-07

    A facile and one-pot approach to the preparation of gold (Au) and copper (Cu) bimetallic nanoclusters (NCs) is unveiled. AuCu NCs reveal features of orange photoluminescence (PL), reversible pH-dependent PL properties, and efficient catalytic activity for degradation of methylene blue (MB).

  20. ENHANCED CORRISION-BASED PD/MG BIMETALLIC SYSTEMS FOR DECHLORINATION OF PCBS

    EPA Science Inventory

    Polychlorinated biphenyls (PCBs) are toxic pollutants notorious for their aquatic and sedimentary prevalence and recalcitrant nature. Bimetallic systems like Pd/Fe have been widely studied for degrading them. Mg, with oxidation potential higher than Fe, has been reported to dechl...

  1. PD/MG BIMETALLIC CORROSION SYSTEMS FOR DECHLORINATION OF PCB CONTAMINATED MATRICES

    EPA Science Inventory

    Polychlorinated biphenyls (PCBs), a family of 209 compounds manufactured till mid70's, are toxic pollutants that persist in the environment. Enhanced corrosion of an active metal combined with catalytic hydrogenation properties of Pd in bimetallic cells can effectively reduce PCB...

  2. Nanostructures having high performance thermoelectric properties

    DOEpatents

    Yang, Peidong; Majumdar, Arunava; Hochbaum, Allon I; Chen, Renkun; Delgado, Raul Diaz

    2014-05-20

    The invention provides for a nanostructure, or an array of such nanostructures, each comprising a rough surface, and a doped or undoped semiconductor. The nanostructure is an one-dimensional (1-D) nanostructure, such a nanowire, or a two-dimensional (2-D) nanostructure. The nanostructure can be placed between two electrodes and used for thermoelectric power generation or thermoelectric cooling.

  3. Nanostructures having high performance thermoelectric properties

    DOEpatents

    Yang, Peidong; Majumdar, Arunava; Hochbaum, Allon I.; Chen, Renkun; Delgado, Raul Diaz

    2015-12-22

    The invention provides for a nanostructure, or an array of such nanostructures, each comprising a rough surface, and a doped or undoped semiconductor. The nanostructure is an one-dimensional (1-D) nanostructure, such a nanowire, or a two-dimensional (2-D) nanostructure. The nanostructure can be placed between two electrodes and used for thermoelectric power generation or thermoelectric cooling.

  4. Thermal decomposition of mono- and bimetallic magnesium amidoborane complexes.

    PubMed

    Spielmann, Jan; Piesik, Dirk F-J; Harder, Sjoerd

    2010-07-26

    Complexes of the type [(DIPPnacnac)MgNH(R)BH(3)] have been prepared (DIPPnacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)). The following substituents R have been used: H, Me, iPr, DIPP (DIPP=2,6-diisopropylphenyl). Complexes [(DIPPnac- nac)MgNH(2)BH(3)].THF, [{(DIPPnac- nac)MgNH(iPr)BH(3)}(2)] and [(DIPPnacnac)MgNH(DIPP)BH(3)] were structurally characterised. The Mg amidoborane complexes decompose at a significantly higher temperature (90-110 degrees C) than the corresponding Ca amidoborane complexes (20-110 degrees C). The complexes with the smaller R substituents (H, Me) gave a mixture of decomposition products of which one could be structurally characterised as [{(DIPPnacnac)Mg}(2)(H(3)B-NMe-BH-NMe)].THF. [{(DIPP- nacnac)MgNH(iPr)BH(3)}(2)] cleanly decomposed to [(DIPPnacnac)MgH], which was characterised as a dimeric THF adduct. The amidoborane complex with the larger DIPP-substituent decomposed into a borylamide complex [(DIPPnacnac)MgN(DIPP)BH(2)], which was structurally characterised as its THF adduct. Bimetallic Mg amidoborane complexes decompose at lower temperatures (60-90 degrees C) and show a different decomposition pathway. The dinuclear Mg amidoborane complexes presented here are based on DIPPnacnac units that are either directly coupled through N-N bonding (abbreviated NN) or through a 2,6-pyridylene bridge (abbreviated PYR). Crystal structures of [PYR-{Mg(nBu)}(2)], [PYR-{MgNH(iPr)BH(3)}(2)], [NN-{MgNH(iPr)BH(3)}(2)]THF and the decomposition products [PYR-Mg(2)(iPrN-BH-iPrN-BH(3))] and [NN-Mg(2)(iPrN-BH-iPrN-BH(3))].THF are presented. The following conclusions can be drawn from these studies: i) The first step in the decomposition of a metal amidoborane complex is beta-hydride elimination, which results in formation of a metal hydride complex and R(H)N=BH(2), ii) depending on the nature of the metal, the metal hydride is either stable and can be isolated or it reacts further, iii) amidoborane anions with small R substituents decompose into the dianionic

  5. Phytogenic silver, gold, and bimetallic nanoparticles as novel antitubercular agents

    PubMed Central

    Singh, Richa; Nawale, Laxman; Arkile, Manisha; Wadhwani, Sweety; Shedbalkar, Utkarsha; Chopade, Snehal; Sarkar, Dhiman; Chopade, Balu Ananda

    2016-01-01

    Purpose Multi- and extensively drug-resistant tuberculosis (TB) is a global threat to human health. It requires immediate action to seek new antitubercular compounds and devise alternate strategies. Nanomaterials, in the present scenario, have opened new avenues in medicine, diagnosis, and therapeutics. In view of this, the current study aims to determine the efficacy of phytogenic metal nanoparticles to inhibit mycobacteria. Methods Silver (AgNPs), gold (AuNPs), and gold–silver bimetallic (Au–AgNPs) nanoparticles synthesized from medicinal plants, such as Barleria prionitis, Plumbago zeylanica, and Syzygium cumini, were tested against Mycobacterium tuberculosis and M. bovis BCG. In vitro and ex vivo macrophage infection model assays were designed to determine minimum inhibitory concentration (MIC) and half maximal inhibitory concentration of nanoparticles. Microscopic analyses were carried out to demonstrate intracellular uptake of nanoparticles in macrophages. Besides this, biocompatibility, specificity, and selectivity of nanoparticles were also established with respect to human cell lines. Results Au–AgNPs exhibited highest antitubercular activity, with MIC of <2.56 μg/mL, followed by AgNPs. AuNPs did not show such activity at concentrations of up to 100 μg/mL. In vitro and ex vivo macrophage infection model assays revealed the inhibition of both active and dormant stage mycobacteria on exposure to Au–AgNPs. These nanoparticles were capable of entering macrophage cells and exhibited up to 45% cytotoxicity at 30 μg/mL (ten times MIC concentration) after 48 hours. Among these, Au–AgNPs synthesized from S. cumini were found to be more specific toward mycobacteria, with their selectivity index in the range of 94–108. Conclusion This is the first study to report the antimycobacterial activity of AuNPs, AgNPs, and Au–AgNPs synthesized from medicinal plants. Among these, Au–AgNPs from S. cumini showed profound efficiency, specificity, and

  6. Development of clad boiler tubes extruded from bimetallic centrifugal castings

    SciTech Connect

    Sponseller, D.L.; Bakker, W.T.; Timmons, G.A.

    1998-04-01

    Wrought tubes of T-11 steel, externally clad with SS310, have been produced by a new method. The alloys were united directly from the molten state by centrifugal casting. In the optimum process, temperatures were controlled to prevent meltback of the SS310 outer layer by the higher melting T-11 stream. Hollow extrusion billets were prepared from the heavy-walled cast bimetallic tubes and successfully hot extruded to 84-mm OD x 64-mm ID tubes, and to 51-mm OD x 38-mm ID tubes. For the most part, thicknesses of the cladding and of the tube wall are rather uniform around the circumference and from end to end of the tubes. Hardness and tensile properties of annealed 51-mm tubes are uniform from end to end of a tube, and between tubes, and readily conform to ASTM A 213; tubes satisfy the flattening and flaring requirements of ASTM A 450. The cladding is metallurgically bonded to be base metal, as revealed by metallography, and by two tests developed for this study: a bond shear strength test and a twist test. In the latter test, rings 3.1 mm in thickness are slotted and severely twisted with a special tool. In tubes made by the optimum process, minute fissures that form adjacent to some of the pressure points during twist testing occupy just 3% of the bond-line length. Cost estimates for commercial production of 51-mm tubes via the centrifugal casting route suggest that such tubes should be considerably less expensive than conventionally clad tubes (extruded from composite billets assembled from heavy-walled wrought tubes). Such tubes should be attractive for the following applications in utility boilers: high-corrosion areas of existing coal-fired boilers, in both steam-generating tubes and superheaters; water walls, screen tubes, and superheater tubes of municipal waste-incineration boilers; future ultra super-critical boilers operating a higher temperatures and pressures; and steam-generating tubes of Syngas coolers of integrated coal gasification power plants.

  7. Effect of calcination temperature on Mg-Al bimetallic oxides as sorbents for the removal of F(-) in aqueous solutions.

    PubMed

    Moriyama, Sayo; Sasaki, Keiko; Hirajima, Tsuyoshi

    2014-01-01

    Bimetallic oxides were synthesized from hydrotalcite using increasing calcination temperatures (873, 1073, 1273 K). These bimetallic oxides were fully characterized and the sorption density of F(-) was investigated. X-ray diffraction patterns for the produced bimetallic oxides showed that MgO was the primary phase within the range of investigated calcination temperatures, but MgO crystallinity increased with calcination temperature and an additional MgAl2O4 phase was formed. In the process of F(-) sorption, the bimetallic oxides were primarily transformed into hydrotalcite with intercalation of F(-). The Higher calcination temperature increased the MgAl2O4 phase, which did not contribute to the immobilization of F(-). These findings show that optimizing the calcination temperature can be used to maximize the sorption density of this material for F(-) removal.

  8. Nanostructured materials in potentiometry.

    PubMed

    Düzgün, Ali; Zelada-Guillén, Gustavo A; Crespo, Gastón A; Macho, Santiago; Riu, Jordi; Rius, F Xavier

    2011-01-01

    Potentiometry is a very simple electrochemical technique with extraordinary analytical capabilities. It is also well known that nanostructured materials display properties which they do not show in the bulk phase. The combination of the two fields of potentiometry and nanomaterials is therefore a promising area of research and development. In this report, we explain the fundamentals of potentiometric devices that incorporate nanostructured materials and we highlight the advantages and drawbacks of combining nanomaterials and potentiometry. The paper provides an overview of the role of nanostructured materials in the two commonest potentiometric sensors: field-effect transistors and ion-selective electrodes. Additionally, we provide a few recent examples of new potentiometric sensors that are based on receptors immobilized directly onto the nanostructured material surface. Moreover, we summarize the use of potentiometry to analyze processes involving nanostructured materials and the prospects that the use of nanopores offer to potentiometry. Finally, we discuss several difficulties that currently hinder developments in the field and some future trends that will extend potentiometry into new analytical areas such as biology and medicine.

  9. Nanostructured materials for hydrogen storage

    DOEpatents

    Williamson, Andrew J.; Reboredo, Fernando A.

    2007-12-04

    A system for hydrogen storage comprising a porous nano-structured material with hydrogen absorbed on the surfaces of the porous nano-structured material. The system of hydrogen storage comprises absorbing hydrogen on the surfaces of a porous nano-structured semiconductor material.

  10. Platinum-palladium bimetallic nanoparticles on graphitic carbon nitride modified carbon black: A highly electroactive and durable catalyst for electrooxidation of alcohols

    NASA Astrophysics Data System (ADS)

    Qian, Huayu; Chen, Shouwen; Fu, Yongsheng; Wang, Xin

    2015-12-01

    A composite catalyst consisting of Pt-Pd bimetallic nanoparticles (NPs) and graphitic carbon nitride (g-C3N4) modified carbon black (CB) is designed and fabricated by a facile two-step approach. The resulting catalyst exhibits unprecedented high catalytic activity and excellent long-term stability for electrooxidation of alcohols (methanol, ethanol, ethylene glycol and glycerol) in alkaline media. The superior electrochemical performance of the composite catalyst is attributed to the specific characteristics of the unique nanostructure and the synergistic effects of individual components, including the complementary roles of Pt (dehydrogenation site) and Pd (removal of CO-like species), the template effect of the planar amino group of g-C3N4 for the dispersed decoration of Pt-Pd NPs, the high specific surface area of CB for the rapid diffusion of electrolyte and removal of the carbonaceous intermediates, as well as the structural stability of the support based on covalent interaction between g-C3N4 and CB for maintaining the durability of the catalytic system.

  11. Nanostructured Biomaterials for Regeneration**

    PubMed Central

    Wei, Guobao; Ma, Peter X.

    2009-01-01

    Biomaterials play a pivotal role in regenerative medicine, which aims to regenerate and replace lost/dysfunctional tissues or organs. Biomaterials (scaffolds) serve as temporary 3D substrates to guide neo tissue formation and organization. It is often beneficial for a scaffolding material to mimic the characteristics of extracellular matrix (ECM) at the nanometer scale and to induce certain natural developmental or/and wound healing processes for tissue regeneration applications. This article reviews the fabrication and modification technologies for nanofibrous, nanocomposite, and nanostructured drug-delivering scaffolds. ECM-mimicking nanostructured biomaterials have been shown to actively regulate cellular responses including attachment, proliferation, differentiation and matrix deposition. Nano-scaled drug delivery systems can be successfully incorporated into a porous 3D scaffold to enhance the tissue regeneration capacity. In conclusion, nano-structured biomateials are a very exciting and rapidly expanding research area, and are providing new enabling technologies for regenerative medicine. PMID:19946357

  12. Synthesis of porphyrin nanostructures

    DOEpatents

    Fan, Hongyou; Bai, Feng

    2014-10-28

    The present disclosure generally relates to self-assembly methods for generating porphyrin nanostructures. For example, in one embodiment a method is provided that includes preparing a porphyrin solution and a surfactant solution. The porphyrin solution is then mixed with the surfactant solution at a concentration sufficient for confinement of the porphyrin molecules by the surfactant molecules. In some embodiments, the concentration of the surfactant is at or above its critical micelle concentration (CMC), which allows the surfactant to template the growth of the nanostructure over time. The size and morphology of the nanostructures may be affected by the type of porphyrin molecules used, the type of surfactant used, the concentration of the porphyrin and surfactant the pH of the mixture of the solutions, and the order of adding the reagents to the mixture, to name a few variables.

  13. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    SciTech Connect

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver H.; Kanoun, Mohammed B.; Scaranto, Jessica; Hedhili, Mohamed N.; Khalid, Syed; Laveille, Paco V.; D'Souza, Lawrence; Clo, Alain; Basset, Jean -Marie

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  14. Controlled Surface Segregation Leads to Efficient Coke-Resistant Nickel/Platinum Bimetallic Catalysts for the Dry Reforming of Methane

    SciTech Connect

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; Anjum, Dalaver H.; Kanoun, Mohammed B.; Scaranto, Jessica; Hedhili, Mohamed N.; Khalid, Syed; Laveille, Paco V.; Lawrence D'Souza; Clo, Alain; Basset, Jean-Marie

    2015-02-03

    The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.

  15. Surface plasmon resonance sensing of a biomarker of Alzheimer disease in an intensity measurement mode with a bimetallic chip

    NASA Astrophysics Data System (ADS)

    Kim, Hyung Jin; Sohn, Young-Soo; Kim, Chang-duk; Jang, Dae-ho

    2016-09-01

    A surface plasmon resonance (SPR) sensor system with a bimetallic chip has been utilized to sense the very low concentration of amyloid-beta (A β)(1-42) by measurement of the reflectance variation. The bimetallic chip was comprised of Au (10 nm) and Ag (40 nm) on Cr (2 nm)-coated BK-7 glass substrate. Protein A was used to efficiently immobilize the antibody of A β(1-42) on the surface of the bimetallic chip. The reflectance curve of the bimetallic chip represented a narrower linewidth compared to that of the conventional gold (Au) chip. The SPR sensor using the bimetallic chip in the intensity interrogation mode acquired the response of A β(1-42) at concentrations of 250, 500, 750 and 1,000 pg/ml. The calibration plot showed a linear relationship between the mean reflectance variation and the A β(1-42) concentration. The results proved that the SPR sensor system with the bimetallic chip in the intensity interrogation mode can successfully detect various concentrations of A β(1-42), including critical concentration, to help diagnose Alzheimer's disease.

  16. Bimetallic gold-silver nanoplate array as a highly active SERS substrate for detection of streptavidin/biotin assemblies.

    PubMed

    Bi, Liyan; Dong, Jian; Xie, Wei; Lu, Wenbo; Tong, Wei; Tao, Lin; Qian, Weiping

    2013-12-17

    The silver-modified gold nanoplate arrays as bimetallic surface-enhanced Raman scattering (SERS) substrates were optimized for the surface-enhanced Raman detection of streptavidin/biotin monolayer assemblies. The bimetallic gold-silver nanoplate arrays were fabricated by coating silver nanoparticles uniformly on the gold nanoplate arrays. Depending on silver nanoparticle coating, the localized surface plasmon resonance (LSPR) peak of the bimetallic gold-silver nanoplate arrays blue-shifted and broadened significantly. The common probe molecule, Niel Blue A sulfate (NBA) was used for testing the SERS activity of the bimetallic gold-silver nanoplate arrays. The SERS intensity increased with the silver nanoparticle coating, due to a large number of hot spots and nanoparticle interfaces. The platforms were tested against a monolayer of streptavidin functionalized over the bimetallic gold-silver nanoplate arrays showing that good quality spectra could be acquired with a short acquisition time. The supramolecular interaction between streptavidin (strep) and biotin showed subsequent modification of Raman spectra that implied a change of the secondary structure of the host biomolecule. And the detection concentration for biotin by this method was as low as 1.0 nM. The enhanced SERS performance of such bimetallic gold-silver nanoplate arrays could spur further interest in the integration of highly sensitive biosensors for rapid, nondestructive, and quantitative bioanalysis, particularly in microfluidics.

  17. Noble metal-based bimetallic nanoparticles: the effect of the structure on the optical, catalytic and photocatalytic properties.

    PubMed

    Zaleska-Medynska, Adriana; Marchelek, Martyna; Diak, Magdalena; Grabowska, Ewelina

    2016-03-01

    Nanoparticles composed of two different metal elements show novel electronic, optical, catalytic or photocatalytic properties from monometallic nanoparticles. Bimetallic nanoparticles could show not only the combination of the properties related to the presence of two individual metals, but also new properties due to a synergy between two metals. The structure of bimetallic nanoparticles can be oriented in random alloy, alloy with an intermetallic compound, cluster-in-cluster or core-shell structures and is strictly dependent on the relative strengths of metal-metal bond, surface energies of bulk elements, relative atomic sizes, preparation method and conditions, etc. In this review, selected properties, such as structure, optical, catalytic and photocatalytic of noble metals-based bimetallic nanoparticles, are discussed together with preparation routes. The effects of preparation method conditions as well as metal properties on the final structure of bimetallic nanoparticles (from alloy to core-shell structure) are followed. The role of bimetallic nanoparticles in heterogeneous catalysis and photocatalysis are discussed. Furthermore, structure and optical characteristics of bimetallic nanoparticles are described in relation to the some features of monometallic NPs. Such a complex approach allows to systematize knowledge and to identify the future direction of research.

  18. Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

    DOE PAGES

    Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

    2015-02-03

    Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

  19. Nanostructured Solar Cells.

    PubMed

    Chen, Guanying; Ning, Zhijun; Ågren, Hans

    2016-08-09

    We are glad to announce the Special Issue "Nanostructured Solar Cells", published in Nanomaterials. This issue consists of eight articles, two communications, and one review paper, covering major important aspects of nanostructured solar cells of varying types. From fundamental physicochemical investigations to technological advances, and from single junction solar cells (silicon solar cell, dye sensitized solar cell, quantum dots sensitized solar cell, and small molecule organic solar cell) to tandem multi-junction solar cells, all aspects are included and discussed in this issue to advance the use of nanotechnology to improve the performance of solar cells with reduced fabrication costs.

  20. Plasmonics in nanostructures.

    PubMed

    Fang, Zheyu; Zhu, Xing

    2013-07-26

    Plasmonics has developed into one of the rapidly growing research topics for nanophotonics. With advanced nanofabrication techniques, a broad variety of nanostructures can be designed and fabricated for plasmonic devices at nanoscale. Fundamental properties for both surface plasmon polaritons (SPP) and localized surface plasmons (LSP) arise a new insight and understanding for the electro-optical device investigations, such as plasmonic nanofocusing, low-loss plasmon waveguide and active plasmonic detectors for energy harvesting. Here, we review some typical functional plasmonic nanostructures and nanosmart devices emerging from our individual and collaborative research works.

  1. Nanostructured Solar Cells

    PubMed Central

    Chen, Guanying; Ning, Zhijun; Ågren, Hans

    2016-01-01

    We are glad to announce the Special Issue “Nanostructured Solar Cells”, published in Nanomaterials. This issue consists of eight articles, two communications, and one review paper, covering major important aspects of nanostructured solar cells of varying types. From fundamental physicochemical investigations to technological advances, and from single junction solar cells (silicon solar cell, dye sensitized solar cell, quantum dots sensitized solar cell, and small molecule organic solar cell) to tandem multi-junction solar cells, all aspects are included and discussed in this issue to advance the use of nanotechnology to improve the performance of solar cells with reduced fabrication costs.

  2. Kinetics and mechanism of the liquid-phase oxidation of cyclohexene. V. Oxidation of cyclohexene in the presence of bimetallic catalysts

    SciTech Connect

    Baevskii, M.Yu.; Litvintsev, I.Yu.; Sapunov, V.N.

    1988-11-01

    The kinetics of the liquid-phase oxidation of cyclohexene in the presence of homogeneous bimetallic catalysts Co-V, Pb-V, Pb-Mo was investigated. It was shown that the activity of the bimetallic catalyst found is determined to a large degree by the nature of the epoxiding metal. A general model is proposed for the oxidation of cyclohexene in the presence of bimetallic catalysts.

  3. Expanding the plasmonic response of bimetallic nanoparticles by laser seeding

    NASA Astrophysics Data System (ADS)

    Peláez, R. J.; Rodríguez, C. E.; Afonso, C. N.

    2016-03-01

    This work explores a cost-effective route to enhance the tuning range of the optical response of metal nanostructures on substrates beyond the ranges that are achievable through the nanostructure dimensions, composition or dewetting processes. The new route (laser seeding) uses single nanosecond laser pulses to induce dewetting in regions of a metal layer deposited on a glass substrate followed by the deposition of a second metal layer, both layers being deposited by pulsed laser deposition. In order to show the possibilities of this new route, we have chosen that the two metals were different, namely Ag and Au. The comparison of the optical response of these regions to those that were laser irradiated after deposition of the second metal layer shows that while nanoalloyed nanoparticles (NPs) are formed in the latter case, the NPs produced in the former case have a heterogeneous structure. The interface between the two metals is either sharp or a narrow region where they have mixed depending on the laser fluence used. While the nanoalloyed NPs exhibit a single, narrow surface plasmon resonance (SPR), the heterogeneous NPs show broader SPRs that peak in the near infrared and depending on conditions exhibit even two clear SPRs. The laser seeding approach in the conditions used in this work allows for the expansion of the tuning range of the color to the blue-green region, i.e. beyond the region that can be achieved through nanoalloyed NPs (yellow-red region). In addition, the results presented foresee the laser seeding route as a means to produce round and almost isolated NPs in an enhanced range of diameters.

  4. Aspartame-stabilized gold-silver bimetallic biocompatible nanostructures with plasmonic photothermal properties, antibacterial activity, and long-term stability.

    PubMed

    Fasciani, Chiara; Silvero, M Jazmin; Anghel, Maria Alexandra; Argüello, Gerardo A; Becerra, Maria Cecilia; Scaiano, Juan C

    2014-12-17

    Gold-silver core-shell nanoparticles stabilized with a common sweetener, aspartame (AuNP@Ag@Asm), combine the antimicrobial properties of silver with the photoinduced plasmon-mediated photothermal effects of gold. The particles were tested with several bacterial strains, while biocompatibility was verified with human dermal fibroblasts.

  5. Low Dimensional Non-Crystallographic Metallic Nanostructures:. HRTEM Simulation, Models and Experimental Results

    NASA Astrophysics Data System (ADS)

    Rodríguez-López, J. L.; Montejano-Carrizales, J. M.; José-Yacamán, M.

    Modern nanoparticle research in the field of small metallic systems has confirmed that many nanoparticles take on some Platonic and Archimedean solids related shapes. A Platonic solid looks the same from any vertex, and intuitively they appear as good candidates for atomic equilibrium shapes. A very clear example is the icosahedral (Ih) particle that only shows {111} faces that contribute to produce a more rounded structure. Indeed, many studies report the Ih as the most stable particle at the size range r≤20 Å for noble gases and for some metals. In this review, we report on the structure and shape of mono- and bimetallic nanoparticles in the wide size range from 1-300 nm. First, we present AuPd nanoparticles in the 1-2 nm size range that show dodecahedral atomic growth packing, one of the Platonic solid shapes that have not been identified before in this small size range for metallic particles. Next, with particles in the size range of 2-5 nm, we present an energetic surface reconstruction phenomenon observed also on bimetallic nanoparticle systems of AuPd and AuCu, similar to a re-solidification effect observed during cooling process in lead clusters. These binary alloy nanoparticles show the fivefold edges truncated, resulting in {100} faces on decahedral structures, an effect largely envisioned and reported theoretically, with no experimental evidence in the literature before. Next nanostructure we review is a monometallic system in the size range of ≈5 nm that we termed the decmon. We present here some detailed geometrical analysis and experimental evidence that supports our models. Finally, in the size range of 100-300 nm, we present icosahedrally derived star gold nanocrystals which resembles the great stellated dodechaedron, which is a Kepler-Poisont solid. We conclude then that the shape or morphology of some mono- and bimetallic particles evolves with size following the sequence from atoms to the Platonic solids, and with a slightly greater particle

  6. Building Nanostructures with Drugs

    PubMed Central

    Ma, Wang; Cheetham, Andrew G.

    2016-01-01

    The convergence of nanoscience and drug delivery has prompted the formation of the field of nanomedicine, one that exploits the novel physicochemical and biological properties of nanostructures for improved medical treatments and reduced side effects. Until recently, this nanostructure-mediated strategy considered the drug to be solely a biologically active compound to be delivered, and its potential as a molecular building unit remained largely unexplored. A growing trend within nanomedicine has been the use of drug molecules to build well-defined nanostructures of various sizes and shapes. This strategy allows for the creation of self-delivering supramolecular nanomedicines containing a high and fixed drug content. Through rational design of the number and type of the drug incorporated, the resulting nanostructures can be tailored to assume various morphologies (e.g. nanospheres, rods, nanofibers, or nanotubes) for a particular mode of administration such as systemic, topical, and local delivery. This review covers the recent advances in this rapidly developing field, with the aim of providing an in-depth evaluation of the exciting opportunities that this new field could create to improve the current clinical practice of nanomedicine. PMID:27066106

  7. Nanostructured catalyst supports

    DOEpatents

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2012-10-02

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  8. Atomically Traceable Nanostructure Fabrication.

    PubMed

    Ballard, Josh B; Dick, Don D; McDonnell, Stephen J; Bischof, Maia; Fu, Joseph; Owen, James H G; Owen, William R; Alexander, Justin D; Jaeger, David L; Namboodiri, Pradeep; Fuchs, Ehud; Chabal, Yves J; Wallace, Robert M; Reidy, Richard; Silver, Richard M; Randall, John N; Von Ehr, James

    2015-07-17

    Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top-down atomic control over nanofabrication. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure.

  9. Emerging double helical nanostructures.

    PubMed

    Zhao, Meng-Qiang; Zhang, Qiang; Tian, Gui-Li; Wei, Fei

    2014-08-21

    As one of the most important and land-mark structures found in nature, a double helix consists of two congruent single helices with the same axis or a translation along the axis. This double helical structure renders the deoxyribonucleic acid (DNA) the crucial biomolecule in evolution and metabolism. DNA-like double helical nanostructures are probably the most fantastic yet ubiquitous geometry at the nanoscale level, which are expected to exhibit exceptional and even rather different properties due to the unique organization of the two single helices and their synergistic effect. The organization of nanomaterials into double helical structures is an emerging hot topic for nanomaterials science due to their promising exceptional unique properties and applications. This review focuses on the state-of-the-art research progress for the fabrication of double-helical nanostructures based on 'bottom-up' and 'top-down' strategies. The relevant nanoscale, mesoscale, and macroscopic scale fabrication methods, as well as the properties of the double helical nanostructures are included. Critical perspectives are devoted to the synthesis principles and potential applications in this emerging research area. A multidisciplinary approach from the scope of nanoscience, physics, chemistry, materials, engineering, and other application areas is still required to the well-controlled and large-scale synthesis, mechanism, property, and application exploration of double helical nanostructures.

  10. Nanostructured catalyst supports

    DOEpatents

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2015-09-29

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  11. Complex WS 2 nanostructures

    NASA Astrophysics Data System (ADS)

    Whitby, R. L. D.; Hsu, W. K.; Lee, T. H.; Boothroyd, C. B.; Kroto, H. W.; Walton, D. R. M.

    2002-06-01

    A range of elegant tubular and conical nanostructures has been created by template growth of (WS 2) n layers on the surfaces of single-walled carbon nanotube bundles. The structures exhibit remarkably perfect straight segments together with interesting complexities at the intersections, which are discussed here in detail in order to enhance understanding of the structural features governing tube growth.

  12. Template-Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal-Organic Frameworks.

    PubMed

    Kim, Daeok; Coskun, Ali

    2017-03-29

    Controlling the arrangement of different metal ions to achieve ordered heterogeneity in metal-organic frameworks (MOFs) has been a great challenge. Herein, we introduce a template-directed approach, in which a 1D metal-organic polymer incorporating well-defined binding pockets for the secondary metal ions used as a structural template and starting material for the preparation of well-ordered bimetallic MOF-74s under heterogeneous-phase hydrothermal reaction conditions in the presence of secondary metal ions such as Ni(2+) and Mg(2+) in 3 h. The resulting bimetallic MOF-74s were found to possess a nearly 1:1 metal ratio regardless of their initial stoichiometry in the reaction mixture, thus demonstrating the possibility of controlling the arrangement of metal ions within the secondary building blocks in MOFs to tune their intrinsic properties such as gas affinity.

  13. Decomposition kinetics of ammonia in gaseous stream by a nanoscale copper-cerium bimetallic catalyst.

    PubMed

    Hung, Chang-Mao

    2008-01-15

    This study performance is to examine the kinetics over nanoscale copper-cerium bimetallic catalyst under selective catalytic oxidation (SCO) of ammonia to N(2) in a tubular fixed-bed reactor (TFBR) at temperatures from 150 to 400 degrees C in the presence of oxygen. The nanoscale copper-cerium bimetallic catalyst was prepared by co-precipitation with Cu(NO(3))(2) and Ce(NO(3))(3) at molar ratio of 6:4. Experimental results showed that the catalyst with transmission electron microscopy (TEM) revealed that copper and cerium are well dispersed and catalyst in the form of nanometer-sized particles. Moreover, the kinetic behavior of NH(3) oxidation with catalysis can be accounted by using the rate expression of the Langmuir-Hinshelwood type kinetic model. Kinetic parameters are also developed on the basis of the differential reactor data. Also, experimental results are compared with those of the model predicted.

  14. Synthesis of a discrete-action thermo-bimetallic actuator with a tongue

    NASA Astrophysics Data System (ADS)

    Nikolaeva, A.; McMillan, AJ; Gavriushin, S.

    2016-10-01

    The selection of suitable parameters, by experimental or intuitive processes for snap-through actuation of a bimetallic actuator at a prescribed temperature is an extremely time-consuming task. This paper describes a new methodology for the optimization of a discrete action thermo-bimetallic actuator with a tongue. This methodology makes it possible to solve the optimization task with higher efficiency. The requirement is to find optimal parameters values so that the actuator will make a snap-through at a given temperature. The constrained optimization task was performed using an evolutional algorithm and surrogate modelling and this was coded in Matlab. Functional relationships between the criteria and parameters were not set explicitly, but they were calculated using finite element method, each simulation of which was performed in Abaqus.

  15. Uncovering the Stabilization Mechanism in Bimetallic Ruthenium-Iridium Anodes for Proton Exchange Membrane Electrolyzers.

    PubMed

    Saveleva, Viktoriia A; Wang, Li; Luo, Wen; Zafeiratos, Spyridon; Ulhaq-Bouillet, Corinne; Gago, Aldo S; Friedrich, K Andreas; Savinova, Elena R

    2016-08-18

    Proton exchange membrane (PEM) electrolyzers are attracting an increasing attention as a promising technology for the renewable electricity storage. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is applied for in situ monitoring of the surface state of membrane electrode assemblies with RuO2 and bimetallic Ir0.7Ru0.3O2 anodes during water splitting. We demonstrate that Ir protects Ru from the formation of an unstable hydrous Ru(IV) oxide thereby rendering bimetallic Ru-Ir oxide electrodes with higher corrosion resistance. We further show that the water splitting occurs through a surface Ru(VIII) intermediate, and, contrary to common opinion, the presence of Ir does not hinder its formation.

  16. Structure and atomic vibrations in bimetallic Ni13 - n Al n clusters

    NASA Astrophysics Data System (ADS)

    Rusina, G. G.; Borisova, S. D.; Chulkov, E. V.

    2015-04-01

    The binding energy, equilibrium geometry, and vibration frequencies in bimetallic clusters Ni13 - n Al n ( n = 0-13) have been calculated using the embedded atom method potentials. It has been shown that the icosahedral structure is the most stable in monoatomic and bimetallic clusters. A tendency of Al atoms to segregate on the cluster surface has been revealed in agreement with the experimental data. The calculations of the atomic vibrations have shown the nonmonotonic dependence of the minimum and maximum vibration frequencies of cluster atoms on its composition and the coupling of their extreme values with the most stable atomic configuration. The increase in the number of Al atoms leads to the shift of the frequency spectrum and the substantial redistribution of the localization of vibrations on the cluster atoms.

  17. Theoretical analysis of D-type optical fiber sensor with a bimetallic layer

    NASA Astrophysics Data System (ADS)

    Liu, Yaobo; Liu, Yueming; Hu, Liaolin

    2008-12-01

    In this paper, we consider a SPR sensor based on D-type optical fiber with bimetallic combination. In pursuit of both higher sensitivity and larger operating range, firstly, we separately analyze the influence of parameters such as the length of coating L, the incident angle θ and the thickness of Au-coating layer d. when the optimum parameters of sensor are determined, we analyze the performance of the sensor with different bimetallic combination consist of Au, Ag, Cu and Al. Lastly, we can get a conclusion that the sensor with L=5mm,d=25nm, θ=88° and Au-Ag at x=0.8 can provide the best performance in terms of the sensitivity and operating range.

  18. Synthesis, characterization, and growth simulations of Cu-Pt bimetallic nanoclusters.

    PubMed

    Khanal, Subarna; Spitale, Ana; Bhattarai, Nabraj; Bahena, Daniel; Velazquez-Salazar, J Jesus; Mejía-Rosales, Sergio; M Mariscal, Marcelo; José-Yacaman, Miguel

    2014-01-01

    Highly monodispersed Cu-Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM) and spherical aberration (C s)-corrected scanning transmission electron microscopy (STEM) images shows that the average diameter of the Cu-Pt nanoclusters is 3.0 ± 1.0 nm. The high angle annular dark field (HAADF-STEM) images, intensity profiles, and energy dispersive X-ray spectroscopy (EDX) line scans, allowed us to study the distribution of Cu and Pt with atomistic resolution, finding that Pt is embedded randomly in the Cu lattice. A novel simulation method is applied to study the growth mechanism, which shows the formation of alloy structures in good agreement with the experimental evidence. The findings give insight into the formation mechanism of the nanosized Cu-Pt bimetallic catalysts.

  19. Nanosized Pd-Au bimetallic phases on carbon nanotubes for selective phenylacetylene hydrogenation.

    PubMed

    Wang, Shenghua; Xin, Zhiling; Huang, Xing; Yu, Weizhen; Niu, Shuo; Shao, Lidong

    2017-02-22

    Palladium (Pd)-catalyzed selective hydrogenation of alkynes has been one of the most studied hydrogenation reactions in the last century. However, kinetic studies conducted to reveal the catalyst's active centers have been hindered because of dynamic surface changes on Pd during the reaction. In the present study, bimetallic Pd-Au nanoparticles supported on carbon nanotubes have been synthesized at room temperature as catalysts for selective hydrogenation of phenylacetylene, which show effectively enhanced selectivity compared to their monometallic counterparts. Structural and surface analyses of fresh and reacted catalysts reveal that selective hydrogenation of phenylacetylene is favored over nanosized Pd-Au bimetallic phases due to modifications in the Pd surface in terms of neighboring site isolation and electron density reduction.

  20. Structural transformation of Au-Pd bimetallic nanoclusters on thermal heating and cooling: a dynamic analysis.

    PubMed

    Liu, H B; Pal, U; Perez, R; Ascencio, J A

    2006-03-23

    Classical molecular dynamics simulation is used for structural thermodynamic and dynamic analysis of Au-Pd bimetallic clusters. It is observed that the Pd-core/Au-shell structure is the most stable, and can be formed through annealing of other structures such as Au-core/Pd-shell, eutecticlike, or solid solution. Depending on the starting temperature and initial composition, three-layer icosahedral nanorod, face-centered cubic (fcc) nanorod, and fcc cluster can be obtained on slow cooling. The three-layer icosahedral nanorod structure is not as stable as the Pd-core/Au-shell decahedron; however it is more stable than the solid-solution decahedron structure up to 400 K. Our findings provide valuable insight into catalysis using Au-Pd and other similar bimetallic clusters.

  1. Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

    SciTech Connect

    Wang, C.; Chi, M.; Li, D.; Strmcnik, D.; van der Vliet, D.; Wang, G.; Komanicky, V.; Chang, K.-C.; Paulikas, A. P.; Tripkovic, D.; Pearson, J.; More, K. L.; Markovic, N. M.; Stamenkovic, V. R.

    2011-01-01

    Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

  2. Design and Synthesis of Bimetallic Electrocatalyst with Multilayered Pt-Skin Surfaces

    SciTech Connect

    Wang, Chao; Chi, Miaofang; Li, Dongguo; Strmcnik, Dusan; Van der Vliet, Dennis; Wang, Guofeng; Komanicky, Vladimir; Chang, Kee-Chul; Paulikas, Arvydas; Tripkovic, Dusan; Pearson, John; More, Karren Leslie; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

  3. Photoluminescent AuCu bimetallic nanoclusters as pH sensors and catalysts

    NASA Astrophysics Data System (ADS)

    Chen, Po-Cheng; Ma, Jia-Ying; Chen, Li-Yi; Lin, Guan-Lin; Shih, Chung-Chien; Lin, Tai-Yuan; Chang, Huan-Tsung

    2014-03-01

    A facile and one-pot approach to the preparation of gold (Au) and copper (Cu) bimetallic nanoclusters (NCs) is unveiled. AuCu NCs reveal features of orange photoluminescence (PL), reversible pH-dependent PL properties, and efficient catalytic activity for degradation of methylene blue (MB).A facile and one-pot approach to the preparation of gold (Au) and copper (Cu) bimetallic nanoclusters (NCs) is unveiled. AuCu NCs reveal features of orange photoluminescence (PL), reversible pH-dependent PL properties, and efficient catalytic activity for degradation of methylene blue (MB). Electronic supplementary information (ESI) available: Experimental section and Fig. S1-S16. See DOI: 10.1039/c3nr06123j

  4. Synthesis, characterization, and growth simulations of Cu–Pt bimetallic nanoclusters

    PubMed Central

    Khanal, Subarna; Spitale, Ana; Bhattarai, Nabraj; Bahena, Daniel; Velazquez-Salazar, J Jesus; Mejía-Rosales, Sergio

    2014-01-01

    Summary Highly monodispersed Cu–Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM) and spherical aberration (C s)-corrected scanning transmission electron microscopy (STEM) images shows that the average diameter of the Cu–Pt nanoclusters is 3.0 ± 1.0 nm. The high angle annular dark field (HAADF-STEM) images, intensity profiles, and energy dispersive X-ray spectroscopy (EDX) line scans, allowed us to study the distribution of Cu and Pt with atomistic resolution, finding that Pt is embedded randomly in the Cu lattice. A novel simulation method is applied to study the growth mechanism, which shows the formation of alloy structures in good agreement with the experimental evidence. The findings give insight into the formation mechanism of the nanosized Cu–Pt bimetallic catalysts. PMID:25247120

  5. Calibrating bimetallic grayscale photomasks to photoresist response for precise micro-optics fabrication

    NASA Astrophysics Data System (ADS)

    Chapman, Glenn H.; Qarehbaghi, Reza; Roche, Santiago

    2014-03-01

    Microfabricating high resolution micro-optics structures requires shape control to <1/8th wavelength (~60nm) in both vertical and horizontal surface precision. Grayscale bimetallic photomasks are bi-layer thermal resists consisting of two thin layers of Bi-on-Indium or Tin-on-Indium. A focused laser spot creates a thermal metal oxide with a controllably transparency set by the beam power of optical density from ~3OD (unexposed) to <0.22OD (fully exposed). A directwrite raster-scan photomask laser system with a CW Argon-ion laser at 514nm for the bimetallic writing and 457nm line for measuring the OD change used a feedback-controlled Gaussian beam to achieve 256-level grayscale masks. Setting the graylevels required to achieve uniform vertical steps in the photoresist requires adjustment in transparency based on the exact response curves of a given resist/development process. An initial model is developed using the classic resist threshold dose exposure D0 and dose to clear Dc creating a power law relation between the required exposure dose for each thickness step and the mask transparency. However real resists behave differently than the simple model near the threshold requiring careful calibrating of mask graylevel transparencies with the photoresist response curve for a given resist/development process. Test structures ranging from steps to ramps and complex patterns were examined via both SEM and profilometry from the resulting bimetallic grayscale masks. Secondary corrections modify the needed bimetallic OD due to the exposure source spectrum differences from the 457nm measurement. This enhances the patterning of micro-optic and 3D MEMS structures.

  6. Platinum-ruthenium bimetallic clusters on graphite: a comparison of vapor deposition and electroless deposition methods.

    PubMed

    Galhenage, Randima P; Xie, Kangmin; Diao, Weijian; Tengco, John Meynard M; Seuser, Grant S; Monnier, John R; Chen, Donna A

    2015-11-14

    Bimetallic Pt-Ru clusters have been grown on highly ordered pyrolytic graphite (HOPG) surfaces by vapor deposition and by electroless deposition. These studies help to bridge the material gap between well-characterized vapor deposited clusters and electrolessly deposited clusters, which are better suited for industrial catalyst preparation. In the vapor deposition experiments, bimetallic clusters were formed by the sequential deposition of Pt on Ru or Ru on Pt. Seed clusters of the first metal were grown on HOPG surfaces that were sputtered with Ar(+) to introduce defects, which act as nucleation sites for Pt or Ru. On the unmodified HOPG surface, both Pt and Ru clusters preferentially nucleated at the step edges, whereas on the sputtered surface, clusters with relatively uniform sizes and spatial distributions were formed. Low energy ion scattering experiments showed that the surface compositions of the bimetallic clusters are Pt-rich, regardless of the order of deposition, indicating that the interdiffusion of metals within the clusters is facile at room temperature. Bimetallic clusters on sputtered HOPG were prepared by the electroless deposition of Pt on Ru seed clusters from a Pt(+2) solution using dimethylamine borane as the reducing agent at pH 11 and 40 °C. After exposure to the electroless deposition bath, Pt was selectively deposited on Ru, as demonstrated by the detection of Pt on the surface by XPS, and the increase in the average cluster height without an increase in the number of clusters, indicating that Pt atoms are incorporated into the Ru seed clusters. Electroless deposition of Ru on Pt seed clusters was also achieved, but it should be noted that this deposition method is extremely sensitive to the presence of other metal ions in solution that have a higher reduction potential than the metal ion targeted for deposition.

  7. Homogeneity and elemental distribution in self-assembled bimetallic Pd-Pt aerogels prepared by a spontaneous one-step gelation process.

    PubMed

    Oezaslan, M; Liu, W; Nachtegaal, M; Frenkel, A I; Rutkowski, B; Werheid, M; Herrmann, A-K; Laugier-Bonnaud, C; Yilmaz, H-C; Gaponik, N; Czyrska-Filemonowicz, A; Eychmüller, A; Schmidt, T J

    2016-07-27

    a commercially available unsupported Pt black catalyst. We show that the Pd-Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

  8. Fabrication of bimetallic microfluidic surface-enhanced Raman scattering sensors on paper by screen printing.

    PubMed

    Qu, Lu-Lu; Song, Qi-Xia; Li, Yuan-Ting; Peng, Mao-Pan; Li, Da-Wei; Chen, Li-Xia; Fossey, John S; Long, Yi-Tao

    2013-08-20

    Au-Ag bimetallic microfluidic, dumbbell-shaped, surface enhanced Raman scattering (SERS) sensors were fabricated on cellulose paper by screen printing. These printed sensors rely on a sample droplet injection zone, and a SERS detection zone at either end of the dumbbell motif, fabricated by printing silver nanoparticles (Ag NPs) and gold nanoparticles (Au NPs) successively with microscale precision. The microfluidic channel was patterned using an insulating ink to connect these two zones and form a hydrophobic circuit. Owing to capillary action of paper in the millimeter-sized channels, the sensor could enable self-filtering of fluids to remove suspended particles within wastewater without pumping. This sensor also allows sensitive SERS detection, due to advantageous combination of the strong surface enhancement of Ag NPs and excellent chemical stability of Au NPs. The SERS performance of the sensors was investigated by employing the probe rhodamine 6G, a limit of detection (LOD) of 1.1×10(-13)M and an enhancement factor of 8.6×10(6) could be achieved. Moreover, the dumbbell-shaped bimetallic sensors exhibited good stability with SERS performance being maintained over 14 weeks in air, and high reproducibility with less than 15% variation in spot-to-spot SERS intensity. Using these dumbbell-shaped bimetallic sensors, substituted aromatic pollutants in wastewater samples could be quantitatively analyzed, which demonstrated their excellent capability for rapid trace pollutant detection in wastewater samples in the field without pre-separation.

  9. Reductive degradation of tetrabromobisphenol A over iron-silver bimetallic nanoparticles under ultrasound radiation.

    PubMed

    Luo, Si; Yang, Shaogui; Wang, Xiaodong; Sun, Cheng

    2010-04-01

    The present study described the degradation behavior of tetrabromobisphenol A (TBBPA) in Fe-Ag suspension solutions under ultrasonic radiation (US). The Fe-Ag bimetallic nanoparticles with core-shell structure were successfully synthesized by reduction and deposition of Ag on nanoscale Fe surface, and were further characterized by BET, XRD, TEM, SEM, X-ray fluorescence and X-ray photo-electron spectroscopy. The results revealed that the displacement plating produced a non-uniform overlayer of Ag additive on iron; the as-synthesized bimetallic nanoparticles were spherical with diameters of 20-100 nm aggregated in the form of chains. Batch studies demonstrated that the TBBPA (2 mg L(-1)) was completely degraded in 20 min over Fe-Ag nanoparticles, which has higher degradation efficiency than Fe(0) nanoparticles under US. The effects of Fe-Ag bimetallic nanoparticles loading, initial TBBPA concentration, pH of the solution, Ag loading and temperature on the reduction efficiency of TBBPA under US were investigated. The complete reduction of TBBPA in 20 min was determined selectively under the conditions of pH (pH=6.0+/-0.5), Ag loading(1 wt.%) at 30 degrees C over the fabricated Fe-Ag nanoparticles. Additionally, the major intermediates identified by LC-MS technique were tri-BBPA, di-BBPA, mono-BBPA and BPA and the degradation mechanism was also proposed.

  10. Prediction of atomic structure of Pt-based bimetallic nanoalloys by using genetic algorithm

    NASA Astrophysics Data System (ADS)

    Oh, Jung Soo; Nam, Ho-Seok; Choi, Jung-Hae; Lee, Seung-Cheol

    2013-05-01

    The atom-arrangements in Pt-based bimetallic nanoalloys were predicted by the combined use of genetic algorithm (GA) and molecular dynamics (MD) simulations. The nanoparticles of these nanoalloys were assumed to be a 3.5 nm-diameter truncated octahedron with Pt and noble metals of fixed composition ratio of 1:1. For the GA, a Python code, which concurrently linked with the MD method that uses the embedded atom method inter-atomic potentials, was developed for the prediction of the atom arrangements in these bimetallic nanoalloys. Successfully, the GA calculation predicted the core-shell structures for both Pt-Ag and Pt-Au nanoalloy, but an onion-like multilayered core-shell structure for Pt-Cu nanoalloy. The structural characteristics in the bimetallic nanoalloy were mainly due to the differences in the surface energy and cohesive energy between Pt and the other alloying metal elements and their miscibility gap and so on. Briefly, the prediction performance was analyzed to show the superior searching ability of GA.

  11. Efficient method for the conversion of agricultural waste into sugar alcohols over supported bimetallic catalysts.

    PubMed

    Tathod, Anup P; Dhepe, Paresh L

    2015-02-01

    Promoter effect of Sn in the PtSn/γ-Al2O3 (AL) and PtSn/C bimetallic catalysts is studied for the conversion of variety of substrates such as, C5 sugars (xylose, arabinose), C6 sugars (glucose, fructose, galactose), hemicelluloses (xylan, arabinogalactan), inulin and agricultural wastes (bagasse, rice husk, wheat straw) into sugar alcohols (sorbitol, mannitol, xylitol, arabitol, galactitol). In all the reactions, PtSn/AL showed enhanced yields of sugar alcohols by 1.5-3 times than Pt/AL. Compared to C, AL supported bimetallic catalysts showed prominent enhancement in the yields of sugar alcohols. Bimetallic catalysts characterized by X-ray diffraction study revealed the stability of catalyst and absence of alloy formation thereby indicating that Pt and Sn are present as individual particles in PtSn/AL. The TEM analysis also confirmed stability of the catalysts and XPS study disclosed formation of electron deficient Sn species which helps in polarizing carbonyl bond to achieve enhanced hydrogenation activity.

  12. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    SciTech Connect

    Chunshan Song; Schobert, H.H.; Parfitt, D.P.

    1997-11-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

  13. Chemical reduction kinetics of nitrate in aqueous solution by Mg/Cu bimetallic particles.

    PubMed

    Mortazavi, S B; Ramavandi, B; Moussavi, G

    2011-01-01

    Synthesized magnesium/copper (Mg/Cu) bimetallic particles have shown good potential for use in the reduction of nitrate from aqueous solutions. This study was conducted to investigate the main factors affecting the kinetics of nitrate reduction by Mg/Cu particles (<100 microm) in uncontrolled reaction conditions. The Mg/Cu bimetallic particles removed the majority of the various nitrate concentrations tested (50, 100, 150, 200 and 300 mg L(-1)) within a short period. The time required for the removal of 90.6% of the NO3(-) from a 100 mg L(-1) solution was about 20 min using 2 gL(-1) bimetallic Mg/Cu at an initial solution pH of 6. The activation energy (Ea) for nitrate reduction by Mg/Cu over the temperature range of 5 to 60 degrees C was 14.21 kJ mol(-1). The experimental results of the kinetic analysis from batch studies indicated that a higher initial nitrate concentration yielded a greater reaction-rate constant and the denitrification rate increased with increase Mg/Cu dosage.

  14. Nanocomposite of bimetallic nanodendrite and reduced graphene oxide as a novel platform for molecular imprinting technology.

    PubMed

    Patra, Santanu; Roy, Ekta; Madhuri, Rashmi; Sharma, Prashant K

    2016-04-28

    In this present work, for the first time, we are reporting a green synthesis approach for the preparation of vinyl modified reduced graphene oxide-based magnetic and bimetallic (Fe/Ag) nanodendrite (RGO@BMNDs). Herein, the RGO@BMNDs acts as a platform for the synthesis of the pyrazinamide (PZA)-imprinted polymer matrix and used for designing of the electrochemical sensor. We have demonstrated how the change in morphology could affect the electrochemical and magnetic property of nanomaterials and for this the reduced graphene oxide-based bimetallic nanoparticle (Fe/Ag) was also prepared It was found that the combination of graphene and bimetallic nanodendrites shows improvement as well as enhancement in the electrocatalytic activity and adsorption capacity, in comparison to their respective nanoparticles. The application of imprinted-RGO@BMNDs sensor was explored for trace level detection of PZA (Limit of detection = 6.65 pg L(-1), S/N = 3), which is a drug used for the cure of Tuberculosis. This is lowest detection limit reported so far for the detection of PZA. The sensor is highly selective, cost-effective, simple and free from any interfering effect. The real time application of the sensor was explored by successful detection of PZA in pharmaceutical and human blood serum, plasma and urine samples.

  15. Bimetallic non-alloyed NPs for improving the broadband optical absorption of thin amorphous silicon substrates

    PubMed Central

    2014-01-01

    We propose the use of bimetallic non-alloyed nanoparticles (BNNPs) to improve the broadband optical absorption of thin amorphous silicon substrates. Isolated bimetallic NPs with uniform size distribution on glass and silicon are obtained by depositing a 10-nm Au film and annealing it at 600°C; this is followed by an 8-nm Ag film annealed at 400°C. We experimentally demonstrate that the deposition of gold (Au)-silver (Ag) bimetallic non-alloyed NPs (BNNPs) on a thin amorphous silicon (a-Si) film increases the film's average absorption and forward scattering over a broad spectrum, thus significantly reducing its total reflection performance. Experimental results show that Au-Ag BNNPs fabricated on a glass substrate exhibit resonant peaks at 437 and 540 nm and a 14-fold increase in average forward scattering over the wavelength range of 300 to 1,100 nm in comparison with bare glass. When deposited on a 100-nm-thin a-Si film, Au-Ag BNNPs increase the average absorption and forward scattering by 19.6% and 95.9% compared to those values for Au NPs on thin a-Si and plain a-Si without MNPs, respectively, over the 300- to 1,100-nm range. PMID:24725390

  16. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    NASA Astrophysics Data System (ADS)

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo; Zhang, Wendong; Zhou, Zhaoying; Yang, Xing; Dong, Hualai; Li, Gang; Hu, Jie

    2014-03-01

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  17. Reaction of 1,1,1-trichloroethane with zero-valent metals and bimetallic reductants

    SciTech Connect

    Fennelly, J.P.; Roberts, A.L.

    1998-07-01

    Information concerning the pathways and products of reaction of 1,1,1-trichloroethane (1,1,1-TCA) with zero-valent metals may be critical to the success of in situ treatment techniques. Many researchers assume that alkyl polyhalides undergo reduction via stepwise hydrogenolysis (replacement of halogen by hydrogen). Accordingly, 1,1,1-TCA should react to 1,1-dichloroethane (1,1-DCA), to chloroethane, and finally to ethane. Experiments conducted in laboratory-scale batch reactors indicate, however, that with zinc, iron, and two bimetallic reductants (nickel-plated iron and copper-plated iron) this simplistic stepwise scheme cannot explain observed results. 1,1,1-TCA was found to react rapidly with zinc to form ethane and 1,1-DCA. Independent experiments confirmed that 1,1-DCA reacts too slowly to represent an intermediate in the formation of ethane. In reactions with iron, nickel/iron, and copper/iron, cis-2-butene, ethylene, and 2-butyne were also observed as minor products. Product ratios were dependent on the identity of the metal or bimetallic reductant, with zinc resulting in the lowest yield of chlorinated product. For reactions with iron and bimetallic reductants, a scheme involving successive one-electron reduction steps to form radicals and carbenoids can be invoked to explain the absence of observable intermediates, as well as the formation of products originating from radical or possibly from carbenoid coupling.

  18. The effect of intermolecular hydrogen bonding on the fluorescence of a bimetallic platinum complex.

    PubMed

    Zhao, Guang-Jiu; Northrop, Brian H; Han, Ke-Li; Stang, Peter J

    2010-09-02

    The bimetallic platinum complexes are known as unique building blocks and arewidely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. Hence, photophysical study of the bimetallic platinum complexes will be very helpful for the understanding on the optical properties and further applications of coordination-driven self-assembled supramolecular metallacycles. Herein, we report steady-state and time-resolved spectroscopic experiments as well as quantum chemistry calculations to investigate the significant intermolecular hydrogen bonding effects on the intramolecular charge transfer (ICT) fluorescence of a bimetallic platinum compound 4,4'-bis(trans-Pt(PEt(3))(2)OTf)benzophenone 3 in solution. We demonstrated that the fluorescent state of compound 3 can be assigned as a metal-to-ligand charge transfer (MLCT) state. Moreover, it was observed that the formation of intermolecular hydrogen bonds can effectively lengthen the fluorescence lifetime of 3 in alcoholic solvents compared with that in hexane solvent. At the same time, the electronically excited states of 3 in solution are definitely changed by intermolecular hydrogen bonding interactions. As a consequence, we propose a new fluorescence modulation mechanism by hydrogen bonding to explain different fluorescence emissions of 3 in hydrogen-bonding solvents and nonhydrogen-bonding solvents.

  19. Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

    SciTech Connect

    Ji, Jianlong; Li, Pengwei; Sang, Shengbo Zhang, Wendong Li, Gang; Hu, Jie; Zhou, Zhaoying Yang, Xing; Dong, Hualai

    2014-03-15

    Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electric field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.

  20. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    PubMed Central

    Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

  1. Ferrocenyl-cymantrenyl hetero-bimetallic chalcones: Synthesis, structure and biological properties

    NASA Astrophysics Data System (ADS)

    Mishra, Sasmita; Tirkey, Vijaylakshmi; Ghosh, Avishek; Dash, Hirak R.; Das, Surajit; Shukla, Madhulata; Saha, Satyen; Mobin, Sheikh M.; Chatterjee, Saurav

    2015-04-01

    Two new ferrocenyl-cymantrenyl bimetallic chalcones, [(CO)3Mn(η5-C5H4)C(O)CHdbnd CH(η5-C5H4)Fe(η5-C5H5)] (1) and [{(CO)3Mn(η5-C5H4)C(O)CHdbnd CH(η5-C5H4)}2Fe] (2) have been synthesized. Their reactivity study with triphenylphosphine and bis-(diphenylphosphino)ferrocene led to the isolation of phosphine substituted bimetallic chalcones (3-6). Single crystal X-ray structural characterization for 1 and its phosphine analogue (3) reveals their different conformational identity with anti-conformation for 1, while syn-conformation for 3. Investigation of antimalarial and antibacterial activities was carried out for compounds 1 and 2 against two strains of Plasmodium falciparum (3D7, K1) and four bacterial strains. TD-DFT calculation was performed for compound 1 and electrochemical properties were studied for bimetallic chalcone compounds by cyclic voltammetric technique.

  2. Experimental and computational investigations of sulfur-resistant bimetallic catalysts for reforming of biomass gasification products

    SciTech Connect

    Rangan, Meghana; Yung, Matthew M.; Medlin, J. William

    2011-11-17

    A combination of density functional theory (DFT) calculations and experimental studies of supported catalysts was used to identify H{sub 2}S-resistant biomass gasification product reforming catalysts. DFT calculations were used to search for bimetallic, nickel-based (1 1 1) surfaces with lower sulfur adsorption energies and enhanced ethylene adsorption energies. These metrics were used as predictors for H{sub 2}S resistance and activity toward steam reforming of ethylene, respectively. Relative to Ni, DFT studies found that the Ni/Sn surface alloy exhibited enhanced sulfur resistance and the Ni/Ru system exhibited an improved ethylene binding energy with a small increase in sulfur binding energy. A series of supported bimetallic nickel catalysts was prepared and screened under model ethylene reforming conditions and simulated biomass tar reforming conditions. The observed experimental trends in activity were consistent with theoretical predictions, with observed reforming activities in the order Ni/Ru > Ni > Ni/Sn. Interestingly, Ni/Ru showed a high level of resistance to sulfur poisoning compared with Ni. This sulfur resistance can be partly explained by trends in sulfur versus ethylene binding energy at different types of sites across the bimetallic surface.

  3. Antibacterial Au nanostructured surfaces

    NASA Astrophysics Data System (ADS)

    Wu, Songmei; Zuber, Flavia; Brugger, Juergen; Maniura-Weber, Katharina; Ren, Qun

    2016-01-01

    We present here a technological platform for engineering Au nanotopographies by templated electrodeposition on antibacterial surfaces. Three different types of nanostructures were fabricated: nanopillars, nanorings and nanonuggets. The nanopillars are the basic structures and are 50 nm in diameter and 100 nm in height. Particular arrangement of the nanopillars in various geometries formed nanorings and nanonuggets. Flat surfaces, rough substrate surfaces, and various nanostructured surfaces were compared for their abilities to attach and kill bacterial cells. Methicillin-resistant Staphylococcus aureus, a Gram-positive bacterial strain responsible for many infections in health care system, was used as the model bacterial strain. It was found that all the Au nanostructures, regardless their shapes, exhibited similar excellent antibacterial properties. A comparison of live cells attached to nanotopographic surfaces showed that the number of live S. aureus cells was <1% of that from flat and rough reference surfaces. Our micro/nanofabrication process is a scalable approach based on cost-efficient self-organization and provides potential for further developing functional surfaces to study the behavior of microbes on nanoscale topographies.We present here a technological platform for engineering Au nanotopographies by templated electrodeposition on antibacterial surfaces. Three different types of nanostructures were fabricated: nanopillars, nanorings and nanonuggets. The nanopillars are the basic structures and are 50 nm in diameter and 100 nm in height. Particular arrangement of the nanopillars in various geometries formed nanorings and nanonuggets. Flat surfaces, rough substrate surfaces, and various nanostructured surfaces were compared for their abilities to attach and kill bacterial cells. Methicillin-resistant Staphylococcus aureus, a Gram-positive bacterial strain responsible for many infections in health care system, was used as the model bacterial strain. It

  4. Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

    SciTech Connect

    Kuila, Debasish; Ilias, Shamsuddin

    2013-02-13

    In steam reforming reactions (SRRs) of alkanes and alcohols to produce H2, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N2 adsorption, and Transmission electron microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m2/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean

  5. Selective Hydrogenation of Phenylacetylene on Bimetallic Cu-Pd and Cu-Pt Catalysts

    NASA Astrophysics Data System (ADS)

    Cladaras, George

    The development of selective catalysts has become a key concept in improving the efficiency of processes. Controlling the product distribution of a reaction can result in fewer by-products and reduce energy requirements for process equipment downstream. The selective hydrogenation of alkynes to alkenes is of major importance to industrial polymerization processes where alkyne/diene impurities can poison the polymerization catalyst and have an unwanted inhibiting effect on the growth of the polymer chain. In many circumstances, bimetallic catalysts have proved to have superior catalytic properties such as greater activity, selectivity or stability compared to their monometallic analogs. A study by the Sykes group (Chemistry, Tufts) in collaboration with our group has shown that in ultra-high vacuum (UHV), the addition of Pd minority species (0.01 ML) onto an otherwise inert Cu(111) single crystal surface can activate the Cu surface for selective hydrogenation reactions. This thesis work is an extension of the surface science study to the preparation of bimetallic catalysts at the nanoscale and their testing in hydrogenation reactions at ambient reaction conditions. The overall aim of this work was to develop single atom alloy Pd-Cu and Pt-Cu catalysts which are highly active and selective for the selective hydrogenation reaction of phenylacetylene to styrene. The bimetallic catalysts were prepared by a colloidal synthesis of Cu nanoparticles immobilized on gamma-alumina support and the precious metals as a minority species were deposited by galvanic replacement. The prepared materials and synthesis technique were characterized with electron microscopy (TEM), UV-Vis spectroscopy, X-Ray diffraction (XRD), temperature programmed reduction (TPR), BET surface area measurements, chemisorption experiments and X-ray photoelectron spectroscopy (XPS). The resulting catalysts can be described as gamma-Al2O3 supported Cu nanoparticles with a narrow size distribution. The Pt

  6. Nanostructured Superhydrophobic Coatings

    SciTech Connect

    2009-03-01

    This factsheet describes a research project that deals with the nanostructured superhydrophobic (SH) powders developed at ORNL. This project seeks to (1) improve powder quality; (2) identify binders for plastics, fiberglass, metal (steel being the first priority), wood, and other products such as rubber and shingles; (3) test the coated product for coating quality and durability under operating conditions; and (4) application testing and production of powders in quantity.

  7. Planar plasmonic chiral nanostructures

    NASA Astrophysics Data System (ADS)

    Zu, Shuai; Bao, Yanjun; Fang, Zheyu

    2016-02-01

    A strong chiral optical response induced at a plasmonic Fano resonance in a planar Au heptamer nanostructure was experimentally and theoretically demonstrated. The scattering spectra show the characteristic narrow-band feature of Fano resonances for both left and right circular polarized lights, with a chiral response reaching 30% at the Fano resonance. Specifically, we systematically investigate the chiral response of planar heptamers with gradually changing the inter-particle rotation angles and separation distance. The chiral spectral characteristics clearly depend on the strength of Fano resonances and the associated near-field optical distributions. Finite element method simulations together with a multipole expansion method demonstrate that the enhanced chirality is caused by the excitation of magnetic quadrupolar and electric toroidal dipolar modes. Our work provides an effective method for the design of 2D nanostructures with a strong chiral response.A strong chiral optical response induced at a plasmonic Fano resonance in a planar Au heptamer nanostructure was experimentally and theoretically demonstrated. The scattering spectra show the characteristic narrow-band feature of Fano resonances for both left and right circular polarized lights, with a chiral response reaching 30% at the Fano resonance. Specifically, we systematically investigate the chiral response of planar heptamers with gradually changing the inter-particle rotation angles and separation distance. The chiral spectral characteristics clearly depend on the strength of Fano resonances and the associated near-field optical distributions. Finite element method simulations together with a multipole expansion method demonstrate that the enhanced chirality is caused by the excitation of magnetic quadrupolar and electric toroidal dipolar modes. Our work provides an effective method for the design of 2D nanostructures with a strong chiral response. Electronic supplementary information (ESI) available

  8. Synergistic effect in the oxidation of benzyl alcohol using citrate-stabilized gold bimetallic nanoparticles supported on alumina

    NASA Astrophysics Data System (ADS)

    Gómez-Villarraga, Fernando; Radnik, Jörg; Martin, Andreas; Köckritz, Angela

    2016-06-01

    Bimetallic nanoparticles (NPs) containing gold and various second metals ( M = Pd, Pt, Cu, and Ag) supported on alumina (AuM/Alumina) were prepared using sodium citrate as stabilizer. In addition, supported monometallic Au/Alumina and Pd/Alumina were synthesized and tested to reveal synergistic effects in the catalytic evaluation of the bimetallic catalysts. The monometallic and bimetallic NPs revealed average sizes below 10 nm. The oxidation of benzyl alcohol with molecular oxygen as oxidant at mild conditions in liquid phase in the absence and presence (toluene or NaOH aqueous solution, 0.2 M) of a solvent was selected as test reaction to evaluate the catalytic properties of the above-mentioned solids. AuPd/Alumina exhibited the best catalytic activity among all bimetallic catalysts using toluene as solvent and under solvent-free conditions, respectively. In comparison to the monometallic catalysts, a synergistic effect with AuPd/Alumina was only evident in the solvent-free reaction. The AuPd/Alumina catalyst was able to oxidize benzyl alcohol selectively depending on the reaction medium into benzaldehyde (toluene or solvent-free) or benzoic acid (NaOH aqueous solution, 0.2 M). However, the catalyst deactivated due to particle growth of the bimetallic AuPd NPs by Ostwald ripening and leaching was not observed in the oxidation using toluene as solvent. The size of the catalytically active NPs, the metal composition of the particles, and the reaction conditions greatly influenced the catalytic oxidation results.

  9. Utilization of greenhouse gases through dry reforming: screening of nickel-based bimetallic catalysts and kinetic studies.

    PubMed

    Fan, Mun-Sing; Abdullah, Ahmad Zuhairi; Bhatia, Subhash

    2011-11-18

    A series of bimetallic catalysts containing nickel supported over MgO-ZrO2 were tested for activity in the dry reforming of carbon dioxide. A nickel-cobalt bimetallic catalyst gave the best performance in terms of conversion and coke resistance from a range of Ni-X bimetallic catalysts, X=Ca, K, Ba, La, and Ce. The nitrogen-adsorption and hydrogen-chemisorption studies showed the Ni-Co bimetallic supported catalyst to have good surface area with high metal dispersion. This contributed to the high catalytic activity, in terms of conversion activity and stability of the catalyst, at an equimolar methane/carbon dioxide feed ratio. The kinetics of methane dry reforming are studied in a fixed-bed reactor over an Ni-Co bimetallic catalyst in the temperature range 700-800 °C by varying the partial pressures of CH4 and CO2. The experimental data were analyzed based on the proposed reaction mechanism using the Langmuir-Hinshelwood kinetic model. The activation energies for methane and carbon dioxide consumption were estimated at 52.9 and 48.1 kJ mol(-1), respectively. The lower value of CO2 activation energy compared to the activation energy of CH4 indicated a higher reaction rate of CO2, which owes to the strong basicity of nanocrystalline support, MgO-ZrO2.

  10. A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes.

    PubMed

    Dorta, Reto; Shimon, Linda J W; Rozenberg, Haim; Ben-David, Yehoshoa; Milstein, David

    2003-05-19

    The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

  11. Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

    SciTech Connect

    B Cheney; J Lauterbach; J Chen

    2011-12-31

    Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structure (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.

  12. Three-dimensional defocused orientation sensing of single bimetallic core-shell gold nanorods as multifunctional optical probes.

    PubMed

    Kim, Geun Wan; Lee, So Young; Ha, Ji Won

    2017-03-13

    Bimetallic core-shell gold nanorods (AuNRs) are promising multifunctional orientation probes that can be employed in biological and physical studies. This paper presents the optical properties of single AuNRs coated with palladium (Pd) and platinum (Pt) under scattering-based dark-field (DF) microscopy. Strong longitudinal plasmon damping was observed for the bimetallic AuNRs due to Pd and Pt metals on the AuNR surface. Despite the strong plasmon damping, the bimetallic AuNRs yielded characteristic doughnut-shaped scattering patterns under defocused DF microscopy. Interestingly, a solid bright spot appeared at the center of the defocused scattering patterns due to strong damping in the longitudinal plasmon and the increased contribution from the transverse dipoles to the image patterns, which was verified further by a simulation study. Furthermore, the defocused scattering field distributions enabled a determination of the three-dimensional (3D) orientations of single bimetallic AuNRs through a pattern-match analysis technique without angular degeneracy. Therefore, deeper insight into the optical properties and defocused scattering patterns of single bimetallic AuNRs is provided, which can be used to develop multifunctional optical probes that are capable of sensing of the 3D orientation of a probe, biomolecules based on LSPR shift, gas and humidity, etc.

  13. Alternative nanostructures for thermophones.

    PubMed

    Aliev, Ali E; Mayo, Nathanael K; Jung de Andrade, Monica; Robles, Raquel O; Fang, Shaoli; Baughman, Ray H; Zhang, Mei; Chen, Yongsheng; Lee, Jae Ah; Kim, Seon Jeong

    2015-05-26

    Thermophones are highly promising for applications such as high-power SONAR arrays, flexible loudspeakers, and noise cancellation devices. So far, freestanding carbon nanotube aerogel sheets provide the most attractive performance as a thermoacoustic heat source. However, the limited accessibility of large-size freestanding carbon nanotube aerogel sheets and other even more exotic materials recently investigated hampers the field. We describe alternative materials for a thermoacoustic heat source with high-energy conversion efficiency, additional functionalities, environmentally friendly, and cost-effective production technologies. We discuss the thermoacoustic performance of alternative nanostructured materials and compare their spectral and power dependencies of sound pressure in air. We demonstrate that the heat capacity of aerogel-like nanostructures can be extracted by a thorough analysis of the sound pressure spectra. The study presented here focuses on engineering thermal gradients in the vicinity of nanostructures and subsequent heat dissipation processes from the interior of encapsulated thermoacoustic projectors. Applications of thermoacoustic projectors for high-power SONAR arrays, sound cancellation, and optimal thermal design, regarding enhanced energy conversion efficiency, are discussed.

  14. Plasmonic Nanostructured Cellular Automata

    NASA Astrophysics Data System (ADS)

    Alkhazraji, Emad; Ghalib, A.; Manzoor, K.; Alsunaidi, M. A.

    2017-03-01

    In this work, we have investigated the scattering plasmonic resonance characteristics of silver nanospheres with a geometrical distribution that is modelled by Cellular Automata using time-domain numerical analysis. Cellular Automata are discrete mathematical structures that model different natural phenomena. Two binary one-dimensional Cellular Automata rules are considered to model the nanostructure, namely rule 30 and rule 33. The analysis produces three-dimensional scattering profiles of the entire plasmonic nanostructure. For the Cellular Automaton rule 33, the introduction of more Cellular Automata generations resulted only in slight red and blue shifts in the plasmonic modes with respect to the first generation. On the other hand, while rule 30 introduced significant red shifts in the resonance peaks at early generations, at later generations however, a peculiar effect is witnessed in the scattering profile as new peaks emerge as a feature of the overall Cellular Automata structure rather than the sum of the smaller parts that compose it. We strongly believe that these features that emerge as a result adopting the different 256 Cellular Automata rules as configuration models of nanostructures in different applications and systems might possess a great potential in enhancing their capability, sensitivity, efficiency, and power utilization.

  15. X-ray Absorption Spectroscopy of Bimetallic Pt-Re Catalysts for Hydrogenolysis of Glycerol to Propanediols

    SciTech Connect

    O Daniel; A DeLaRiva; E Kunkes; A Datye; J Dumesic; R Davis

    2011-12-31

    Bimetallic Pt-Re nanoparticles supported on Norit carbon were effective at converting aqueous glycerol to 1,3 (34 %) and 1,2 (33 %) propanediol at 443 K under 4 MPa of H{sub 2}. Results from X-ray absorption spectroscopy and analytical transmission electron microscopy confirmed that the nanoparticles were indeed bimetallic, with a particle size less than 2 nm in diameter. The Pt L{sub III} near edge spectra indicated that the Pt was reduced to the metallic state by treatment in H{sub 2} at 473 K, but that a partial positive charge remained on the Re. These oxidized Re species could be associated with charged Re atoms dispersed on the carbon support because spillover of H atoms from Pt was required to reduce Re in the bimetallic particles.

  16. Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

    SciTech Connect

    Yang, Ying; Gao, Guang; Zhang, Xin; Li, Fuwei

    2016-02-04

    Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (RuxNi1–x–OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophase before pyrolysis and silica removal. The resulting RuxNi1–x–OMC materials are in-depth characterized with X-ray diffraction, N2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru0.9Ni0.1–OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h–1) was obtained, and the Ru0.9Ni0.1–OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.

  17. The synergistic effect in the Fe-Co bimetallic catalyst system for the growth of carbon nanotube forests

    SciTech Connect

    Hardeman, D.; Esconjauregui, S. Cartwright, R.; D'Arsié, L.; Robertson, J.; Bhardwaj, S.; Cepek, C.; Oakes, D.; Clark, J.; Ducati, C.

    2015-01-28

    We report the growth of multi-walled carbon nanotube forests employing an active-active bimetallic Fe-Co catalyst. Using this catalyst system, we observe a synergistic effect by which—in comparison to pure Fe or Co—the height of the forests increases significantly. The homogeneity in the as-grown nanotubes is also improved. By both energy dispersive spectroscopy and in-situ x-ray photoelectron spectroscopy, we show that the catalyst particles consist of Fe and Co, and this dramatically increases the growth rate of the tubes. Bimetallic catalysts are thus potentially useful for synthesising nanotube forests more efficiently.

  18. Controlled synthesis and synergistic effects of graphene-supported PdAu bimetallic nanoparticles with tunable catalytic properties

    NASA Astrophysics Data System (ADS)

    Liu, Chang-Hai; Liu, Rui-Hua; Sun, Qi-Jun; Chang, Jian-Bing; Gao, Xu; Liu, Yang; Lee, Shuit-Tong; Kang, Zhen-Hui; Wang, Sui-Dong

    2015-03-01

    Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical to the catalysis of reduction reaction. By the present method, the bimetallic combination can be tailored for distinct types of catalytic reactions.Graphene-supported bimetallic nanoparticles are promising nanocatalysts, which can show strong and tunable catalytic activity and selectivity. Herein room-temperature-ionic-liquid-assisted metal sputtering is utilized to synthesize PdAu bimetallic nanoparticles on graphene with bare surface, small size, high surface density and controlled Pd-to-Au ratio. This controllable synthetic approach is green-chemistry compatible and totally free of additives and byproducts. The supported PdAu nanoparticles show excellent catalytic capabilities for both oxidation and reduction reactions, strongly dependent on the Pd-to-Au ratio. A strong correlation among catalytic performance, bimetallic composition and charge redistribution in the PdAu nanoparticles has been demonstrated. The results suggest that sufficient Au d-holes appear to be significant to the catalysis of oxidation reaction, and a metallic Pd surface is critical

  19. Nanostructures for peroxidases

    PubMed Central

    Carmona-Ribeiro, Ana M.; Prieto, Tatiana; Nantes, Iseli L.

    2015-01-01

    Peroxidases are enzymes catalyzing redox reactions that cleave peroxides. Their active redox centers have heme, cysteine thiols, selenium, manganese, and other chemical moieties. Peroxidases and their mimetic systems have several technological and biomedical applications such as environment protection, energy production, bioremediation, sensors and immunoassays design, and drug delivery devices. The combination of peroxidases or systems with peroxidase-like activity with nanostructures such as nanoparticles, nanotubes, thin films, liposomes, micelles, nanoflowers, nanorods and others is often an efficient strategy to improve catalytic activity, targeting, and reusability. PMID:26389124

  20. Surface plasmon polariton assisted optical switching in noble bimetallic nanoparticle system

    SciTech Connect

    Dhara, Sandip E-mail: chenkh@pub.iams.sinica.edu.tw; Lu, C.-Y.; Tu, W.-S.; Magudapathy, P.; Huang, Y.-F.; Chen, K.-H. E-mail: chenkh@pub.iams.sinica.edu.tw

    2015-01-12

    Photoresponse of bimetallic Au-Ag nanoparticle embedded soda glass (Au-Ag@SG) substrate is reported for surface plasmon assisted optical switching using 808 nm excitation. Au-Ag@SG system is made by an ion beam technique where Ag{sup +} is introduced first in the soda glass matrix by ion exchange technique. Subsequently, 400 keV Au{sup +} is implanted in the sample for different fluences, which is followed by an ion beam annealing process using 1 MeV Si{sup +} at a fixed fluence of 2 × 10{sup 16} ions·cm{sup −2}. Characteristic surface plasmon resonance (SPR) peaks around 400 and 550 nm provided evidence for the presence of Au and Ag nanoparticles. An optical switching in the Au-Ag@SG system with 808 nm, which is away from the characteristic SPR peaks of Ag and Au nanoparticles, suggests the possible role of two photon absorption (TPA) owing to the presence of interacting electric dipole in these systems. The role of surface plasmon polariton is emphasized for the propagation of electronic carrier belonging to the conduction electron of Au-Ag system in understanding the observed photoresponse. Unique excitation dependent photoresponse measurements confirm the possible role of TPA process. A competitive interband and intraband transitions in the bimetallic system of Au and Ag, which may be primarily responsible for the observation, are validated qualitatively using finite difference time domain calculations where inter-particle separation of Au and Ag plays an important role. Thus, a smart way of optical switching can be envisaged in noble bimetallic nanocluster system where long wavelength with higher skin depth can be used for communication purpose.

  1. Synthesis and ECL performance of highly efficient bimetallic ruthenium tris-bipyridyl complexes.

    PubMed

    Sun, Shiguo; Li, Fusheng; Liu, Fengyu; Yang, Xue; Fan, Jiangli; Song, Fengling; Sun, Licheng; Peng, Xiaojun

    2012-10-28

    In order to find the ideal carbon chain linkage number n for achieving the highest ECL in bimetallic ruthenium tris-bipyridyl complexes, a series of novel complexes [(bpy)(2)Ru(bpy')(CH(2))(n)(bpy')Ru(bpy)(2)](4+) (, where bpy is 2,2'-bipyridyl, n = 10, 12, 14) for a coreactant electrochemiluminescence (ECL) system have been synthesized. Their ECL properties at a Au electrode have been studied in 0.1 M phosphate buffer by using tripropylamine (TPrA), 2-(dibutylamino)ethanol (DBAE) and melamine as the coreactant, to compare with that of the previously reported bimetallic ruthenium analogous complex [(bpy)(2)Ru(bpy')(CH(2))(8)(bpy')Ru(bpy)(2)](4+). The results demonstrate that the ECL intensity depends largely on the length of the saturated carbon chain linkage number n. The highest ECL is reached when n = 10, suggesting that a synergistic effect on ECL enhancement co-exists between the two intramolecular linked ruthenium activating centers. Density functional theory (DFT) calculation demonstrated that the optimized bond distances between Ru and N(bpy') are the longest both in the ground and the excited triplet states in the case of n = 10, while those for Ru and N(bpy) are the shortest in the excited triplet states. All these factors may be responsible for the above mentioned results. This study provided a methodology to further improve and tune ECL efficiency by using bimetallic ruthenium complexes linked by a flexible saturated carbon chain.

  2. Electrical performances of pyroelectric bimetallic strip heat engines describing a Stirling cycle

    NASA Astrophysics Data System (ADS)

    Arnaud, A.; Boughaleb, J.; Monfray, S.; Boeuf, F.; Cugat, O.; Skotnicki, T.

    2015-12-01

    This paper deals with the analytical modeling of pyroelectric bimetallic strip heat engines. These devices are designed to exploit the snap-through of a thermo-mechanically bistable membrane to transform a part of the heat flowing through the membrane into mechanical energy and to convert it into electric energy by means of a piezoelectric layer deposited on the surface of the bistable membrane. In this paper, we describe the properties of these heat engines in the case when they complete a Stirling cycle, and we evaluate the performances (available energy, Carnot efficiency...) of these harvesters at the macro- and micro-scale.

  3. Enhanced antibacterial activity of bimetallic gold-silver core-shell nanoparticles at low silver concentration

    NASA Astrophysics Data System (ADS)

    Banerjee, Madhuchanda; Sharma, Shilpa; Chattopadhyay, Arun; Ghosh, Siddhartha Sankar

    2011-12-01

    Herein we report the development of bimetallic Au@Ag core-shell nanoparticles (NPs) where gold nanoparticles (Au NPs) served as the seeds for continuous deposition of silver atoms on its surface. The core-shell structure and morphology were examined by UV-Vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD). The core-shell NPs showed antibacterial activity against both Gram negative (Escherichia coli and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis and Pediococcus acidilactici) bacteria at low concentration of silver present in the shell, with more efficacy against Gram negative bacteria. TEM and flow cytometric studies showed that the core-shell NPs attached to the bacterial surface and caused membrane damage leading to cell death. The enhanced antibacterial properties of Au@Ag core-shell NPs was possibly due to the more active silver atoms in the shell surrounding gold core due to high surface free energy of the surface Ag atoms owing to shell thinness in the bimetallic NP structure.Herein we report the development of bimetallic Au@Ag core-shell nanoparticles (NPs) where gold nanoparticles (Au NPs) served as the seeds for continuous deposition of silver atoms on its surface. The core-shell structure and morphology were examined by UV-Vis spectroscopy, transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD). The core-shell NPs showed antibacterial activity against both Gram negative (Escherichia coli and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis and Pediococcus acidilactici) bacteria at low concentration of silver present in the shell, with more efficacy against Gram negative bacteria. TEM and flow cytometric studies showed that the core-shell NPs attached to the bacterial surface and caused membrane damage leading to cell death. The enhanced antibacterial properties of Au@Ag core-shell NPs was

  4. Simulation of the interaction of bipartite bimetallic clusters with low-energy argon clusters

    NASA Astrophysics Data System (ADS)

    Shyrokorad, D. V.; Kornich, G. V.; Buga, S. G.

    2017-01-01

    Molecular-dynamics simulation of the evolution of bipartite bimetallic clusters consisting of 390 atoms during bombardment by Arn ( n = 1, 2, 13) clusters with initial energies from 1 eV to 1.4 keV is performed. Binary Cu-Au and Ni-Al clusters consisting of equal atomic fractions of corresponding elements were used as a target. As a result of simulation, the temperatures, changes in the potential energy, sputtering yields, and intensities of collision-stimulated displacement of atoms through the interface of monometallic parts of binary clusters, depending on the size and energy of incident particle, are obtained.

  5. Unprecedented Carbonato Intermediates in Cyclic Carbonate Synthesis Catalysed by Bimetallic Aluminium(Salen) Complexes.

    PubMed

    Castro-Osma, José A; North, Michael; Offermans, Willem K; Leitner, Walter; Müller, Thomas E

    2016-04-21

    The mechanism by which [Al(salen)]2 O complexes catalyse the synthesis of cyclic carbonates from epoxides and carbon dioxide in the absence of a halide cocatalyst has been investigated. Density functional theory (DFT) studies, mass spectrometry and (1) H NMR, (13) C NMR and infrared spectroscopies provide evidence for the formation of an unprecedented carbonato bridged bimetallic aluminium complex which is shown to be a key intermediate for the halide-free synthesis of cyclic carbonates from epoxides and carbon dioxide. Deuterated and enantiomerically-pure epoxides were used to study the reaction pathway. Based on the experimental and theoretical results, a catalytic cycle is proposed.

  6. A molecular metal ferromagnet from the organic donor bis(ethylenedithio)tetraselenafulvalene and bimetallic oxalate complexes.

    PubMed

    Alberola, Antonio; Coronado, Eugenio; Galán-Mascarós, José R; Giménez-Saiz, Carlos; Gómez-García, Carlos J

    2003-09-10

    A new dual-function hybrid molecular material has been obtained from the organic donor bis(ethylenedithio)tetraselenafulvalene and the honeycomb oxalate-based bimetallic network [MnCr(ox)3]-. This multilayer material consists of layers of the inorganic anionic 2D network, responsible for the appearance of ferromagnetic ordering below 5.3 K, alternating with segregated layers of the organic cation radical responsible for the transport properties: metal-like conductivity is observed from room temperature down to 150 K.

  7. Bimetallic PtxCoy nanoparticles with curved faces for highly efficient hydrogenation of cinnamaldehyde

    NASA Astrophysics Data System (ADS)

    Gu, Yan; Zhao, Yonghui; Wu, Panpan; Yang, Bo; Yang, Nating; Zhu, Yan

    2016-05-01

    The control of the curved structure of bimetallic nanocrystals is a challenge, due to the rate differential for atom deposition and surface diffusion of alien atomic species on specific crystallographic planes of seeds. Herein, we report how to tune the degree of concavity of bimetallic PtxCoy concave nanoparticles using carboxylic acids as surfactants with an oleylamine system, leading to the specific crystallographic planes being exposed. The terminal carboxylic acids with a bridge ring or a benzene ring serving as structure regulators could direct the formation of curved faces with exposed high-index facets, and long-chain saturated fatty acids favored the production of curved faces with exposed low-index facets, while long-chain olefin acids alone benefited the formation of a flat surface with exposed low-index planes. Furthermore, these PtxCoy particles with curved faces displayed superior catalytic behaviour to cinnamaldehyde hydrogenation when compared with PtxCoy with flat faces. PtxCoy nanoparticles with curved faces exhibited over 6-fold increase in catalytic activity compared to PtxNiy nanoparticles with curved faces, and near 40-fold activity increase was observed in comparison with PtxFey nanoparticles with curved faces.The control of the curved structure of bimetallic nanocrystals is a challenge, due to the rate differential for atom deposition and surface diffusion of alien atomic species on specific crystallographic planes of seeds. Herein, we report how to tune the degree of concavity of bimetallic PtxCoy concave nanoparticles using carboxylic acids as surfactants with an oleylamine system, leading to the specific crystallographic planes being exposed. The terminal carboxylic acids with a bridge ring or a benzene ring serving as structure regulators could direct the formation of curved faces with exposed high-index facets, and long-chain saturated fatty acids favored the production of curved faces with exposed low-index facets, while long

  8. Bimetallic platinum-iron electrocatalyst supported on carbon fibers for coal electrolysis

    NASA Astrophysics Data System (ADS)

    Yu, Ping; Botte, Gerardine G.

    2015-01-01

    A novel bimetallic Pt-Fe electrode supported on carbon fibers (CFs) was prepared by chemical impregnation/reduction and evaluated for the electrolysis of coal to produce hydrogen. Characterization of the electrocatalyst was performed using X-ray Diffraction, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy. The synthesized Pt-Fe particles were well dispersed on the surface of the CFs. The addition of Fe to the catalyst enhanced the electrooxidation of coal when compared to Pt alone. PtFe (1:1) supported on carbon fibers exhibited superior catalytic activity towards the conversion of coal than PtFe (7:3) and PtFe (3:7).

  9. Synthesis of bimetallic gold/silver nanoparticles via in situ seeding

    NASA Astrophysics Data System (ADS)

    Gorbachevskiy, M. V.; Kopitsyn, D. S.; Tiunov, I. A.; Kotelev, M. S.; Vinokurov, V. A.; Novikov, A. A.

    2017-01-01

    A way of synthesizing bimetallic gold/silver nanoparticles with in situ seeding initiated by the addition of sodium borohydride is proposed. The obtained nanoparticles are studied by means of transmission electron microscopy (TEM). Changes in the optical density spectra of the nanoparticles during their coagulation are investigated. The technique allows the rapid acquisition of nontoxic SERS-active nanoparticles with maximum SERS enhancement factor about 105 in the near infrared range for Raman shifts typical for biological objects such as bacterial cells and spores.

  10. Formation of Pd/Au Nanostructures from Pd Nanowires via Galvanic Replacement Reaction

    SciTech Connect

    Teng,X.; Wang, Q.; Liu, P.; Han, W.; Frenkel, A.; Wen, W.; Marinkovic, N.; Hanson, J.; Rodriguez, J.

    2008-01-01

    Bimetallic nanostructures with non-random metal atoms distribution are very important for various applications. To synthesize such structures via benign wet chemistry approach remains challenging. This paper reports a synthesis of a Au/Pd alloy nanostructure through the galvanic replacement reaction between Pd ultrathin nanowires (2.4 {+-} 0.2 nm in width, over 30 nm in length) and AuCl3 in toluene. Both morphological and structural changes were monitored during the reaction up to 10 h. Continuous changes of chemical composition and crystalline structure from Pd nanowires to Pd68Au32 and Pd45Au55 alloys, and to Au nanoparticles were observed. More interestingly, by using combined techniques such as high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS), UV-vis absorption, and extended X-ray absorption fine structure (EXAFS) spectroscopy, we found the formation of Pd68Au32 non-random alloy with Au-rich core and Pd-rich shell, and random Pd45Au55 alloy with uniformly mixed Pd and Au atom inside the nanoparticles, respectively. Density functional theory (DFT) calculations indicated that alkylamine will strongly stabilize Pd to the surface, resulting in diffusion of Au atoms into the core region to form a non-random alloy. We believe such benign synthetic techniques can also enable the large scale preparation of various types of non-random alloys for several technically important catalysis applications.

  11. Nanofaceted C/Re(1121): fabrication, structure, and template for synthesizing nanostructured model Pt electrocatalyst for hydrogen evolution reaction.

    PubMed

    Yang, Xiaofang; Koel, Bruce E; Wang, Hao; Chen, Wenhua; Bartynski, Robert A

    2012-02-28

    We report the first observation of carbon-induced nanofaceting of a Re single crystal and its application in synthesizing a nanostructured model Pt electrocatalyst investigated using multiple surface science techniques, including low-energy electron diffraction, Auger electron spectroscopy, X-ray photoelectron spectroscopy, low-energy ion scattering, and scanning tunneling microscopy, combined with electrochemical reaction measurements. Upon annealing in acetylene at 700 K followed by annealing in vacuum at 1100 K, an initially planar Re(112̅1) surface becomes completely faceted and covered with three-sided nanopyramids exposing (011̅1), (101̅1), and (112̅0) faces. Using the faceted C/Re(112̅1) surface as a template, we have successfully fabricated a nanostructured Pt monolayer (ML) electrocatalyst. The Pt ML supported on the C/Re nanotemplate exhibits higher activity for the hydrogen evolution reaction than Pt(111). This is the first application of faceted metal surfaces as templates for synthesis of nanoscale model electrocatalyst with well-defined (facet) surface structure and controlled (facet) size on the nanometer scale, illustrating the potential for future studies of nanostructured bimetallic systems relevant to electrocatalytic reactions.

  12. The role of nanostructures and hydrophilicity in osseointegration: In-vitro protein-adsorption and blood-interaction studies.

    PubMed

    Kopf, Brigitte S; Ruch, Sylvie; Berner, Simon; Spencer, Nicholas D; Maniura-Weber, Katharina

    2015-08-01

    Protein adsorption and blood coagulation play important roles in the early stages of osseointegration and are strongly influenced by surface properties. We present a systematic investigation of the influence of different surface properties on the adsorption of the blood proteins fibrinogen and fibronectin and the degree of early blood coagulation. Experiments on custom-made and commercially available, microroughened hydrophobic titanium (Ti) surfaces (Ti SLA-Hphob ), hydrophilic (Hphil ) microroughened Ti surfaces with nanostructures (Ti SLActive-Hphil NS), and on bimetallic Ti zirconium alloy (TiZr, Roxolid®) samples were performed, to study the biological response in relation to the surface wettability and the presence of nanostructures (NS). Protein adsorption on the different substrates showed a highly significant effect of surface NS. Hydrophilicity alone did not significantly enhance protein adsorption. Overall, the combination of NS and hydrophilicity led to the highest adsorption levels; independent of whether Ti or TiZr were used. Hydrophilicity induced a strong effect on blood coagulation, whereas the effect of NS alone was weak. The combination of both surface characteristics led to early and most pronounced blood-coagulation. Therefore, nanostructured, hydrophilic Ti and TiZr surfaces may perform better in terms of osseointegration due to continuous protein adsorption and the formation of a layer of blood components on the implant surface.

  13. Unraveling Surface Plasmon Decay in Core-Shell Nanostructures toward Broadband Light-Driven Catalytic Organic Synthesis.

    PubMed

    Huang, Hao; Zhang, Lei; Lv, Zhiheng; Long, Ran; Zhang, Chao; Lin, Yue; Wei, Kecheng; Wang, Chengming; Chen, Lu; Li, Zhi-Yuan; Zhang, Qun; Luo, Yi; Xiong, Yujie

    2016-06-01

    Harnessing surface plasmon of metal nanostructures to promote catalytic organic synthesis holds great promise in solar-to-chemical energy conversion. High conversion efficiency relies not only on broadening the absorption spectrum but on coupling the harvested energy into chemical reactions. Such coupling undergoes hot-electron transfer and photothermal conversion during the decay of surface plasmon; however, the two plasmonic effects are unfortunately entangled, making their individual roles still under debate. Here, we report that in a model system of bimetallic Au-Pd core-shell nanostructures the two effects can be disentangled through tailoring the shell thickness at atomic-level precision. As demonstrated by our ultrafast absorption spectroscopy characterizations, the achieved tunability of the two effects in a model reaction of Pd-catalyzed organic hydrogenation offers a knob for enhancing energy coupling. In addition, the two intrinsic plasmonic modes at 400-700 and 700-1000 nm in the bar-shaped nanostructures allow for utilizing photons to a large extent in full solar spectrum. This work establishes a paradigmatic guidance toward designing plasmonic-catalytic nanomaterials for enhanced solar-to-chemical energy conversion.

  14. Formation of nanostructured porous Cu-Au surfaces: the influence of cationic sites on (electro)-catalysis

    NASA Astrophysics Data System (ADS)

    Najdovski, Ilija; Selvakannan, Pr.; Bhargava, Suresh K.; O'Mullane, Anthony P.

    2012-09-01

    The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu-Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials. Interestingly, the surface is dominated by Au(i) oxide species incorporated within a Cu2O matrix which is extremely effective for the industrially important (electro)-catalytic reduction of 4-nitrophenol. It is proposed that an aurophilic type of interaction takes place between both oxidized gold and copper species which stabilizes the surface against further oxidation and facilitates the binding of 4-nitrophenol to the surface and increases the rate of reaction. An added benefit is that very low gold loadings are required typically less than 2 wt% for a significant enhancement in performance to be observed. Therefore the ability to create a partially oxidized Cu-Au surface through a facile electrochemical route that uses a clean template consisting of only hydrogen bubbles should be of benefit for many more important reactions.The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu-Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials

  15. EDITORIAL: Nanostructured solar cells Nanostructured solar cells

    NASA Astrophysics Data System (ADS)

    Greenham, Neil C.; Grätzel, Michael

    2008-10-01

    Conversion into electrical power of even a small fraction of the solar radiation incident on the Earth's surface has the potential to satisfy the world's energy demands without generating CO2 emissions. Current photovoltaic technology is not yet fulfilling this promise, largely due to the high cost of the electricity produced. Although the challenges of storage and distribution should not be underestimated, a major bottleneck lies in the photovoltaic devices themselves. Improving efficiency is part of the solution, but diminishing returns in that area mean that reducing the manufacturing cost is absolutely vital, whilst still retaining good efficiencies and device lifetimes. Solution-processible materials, e.g. organic molecules, conjugated polymers and semiconductor nanoparticles, offer new routes to the low-cost production of solar cells. The challenge here is that absorbing light in an organic material produces a coulombically bound exciton that requires dissociation at a donor-acceptor heterojunction. A thickness of at least 100 nm is required to absorb the incident light, but excitons only diffuse a few nanometres before decaying. The problem is therefore intrinsically at the nano-scale: we need composite devices with a large area of internal donor-acceptor interface, but where each carrier has a pathway to the respective electrode. Dye-sensitized and bulk heterojunction cells have nanostructures which approach this challenge in different ways, and leading research in this area is described in many of the articles in this special issue. This issue is not restricted to organic or dye-sensitized photovoltaics, since nanotechnology can also play an important role in devices based on more conventional inorganic materials. In these materials, the electronic properties can be controlled, tuned and in some cases completely changed by nanoscale confinement. Also, the techniques of nanoscience are the natural ones for investigating the localized states, particularly at

  16. Mechanical design of DNA nanostructures.

    PubMed

    Castro, Carlos E; Su, Hai-Jun; Marras, Alexander E; Zhou, Lifeng; Johnson, Joshua

    2015-04-14

    Structural DNA nanotechnology is a rapidly emerging field that has demonstrated great potential for applications such as single molecule sensing, drug delivery, and templating molecular components. As the applications of DNA nanotechnology expand, a consideration of their mechanical behavior is becoming essential to understand how these structures will respond to physical interactions. This review considers three major avenues of recent progress in this area: (1) measuring and designing mechanical properties of DNA nanostructures, (2) designing complex nanostructures based on imposed mechanical stresses, and (3) designing and controlling structurally dynamic nanostructures. This work has laid the foundation for mechanically active nanomachines that can generate, transmit, and respond to physical cues in molecular systems.

  17. Formation of single-walled bimetallic coinage alloy nanotubes in confined carbon nanotubes: molecular dynamics simulations.

    PubMed

    Han, Yang; Zhou, Jian; Dong, Jinming; Yoshiyuki, Kawazoe

    2013-10-28

    The growth of single-walled bimetallic Au-Ag, Au-Cu and Ag-Cu alloy nanotubes (NTs) and nanowires (NWs) in confined carbon nanotubes (CNTs) has been investigated by using the classical molecular dynamics (MD) method. It is found that three kinds of single-walled gold-silver, gold-copper and silver-copper alloy NTs could indeed be formed in confined CNTs at any alloy concentration, whose geometric structures are less sensitive to the alloy concentration. And an extra nearly pure Au (Cu) chain will exist at the center of Au-Ag (Au-Cu and Ag-Cu) NTs when the diameters of the outside CNTs are big enough, thus producing a new type of tube-like alloy NWs. The bonding energy differences between the mono- and hetero-elements of the coinage metal atoms and the quasi-one-dimensional confinement from the CNT play important roles in suppressing effectively the "self-purification" effects, leading to formation of these coinage alloy NTs. In addition, the fluid-solid phase transition temperatures of the bimetallic alloy NTs are found to locate between those of the corresponding pure metal tubes. Finally, the dependences of the radial breathing mode (RBM) frequencies and the tube diameters of the alloy NTs on the alloying concentration were obtained, which will be very helpful for identifying both the alloying concentration and the alloy tube diameters in future experiments.

  18. Dodecanethiol-protected copper/silver bimetallic nanoclusters and their surface properties.

    PubMed

    Ang, T P; Chin, W S

    2005-12-01

    Dodecanethiol-protected copper/silver bimetallic nanoclusters were prepared by a liquid-phase method using different copper to silver feed ratios. The morphology and size of the prepared nanoclusters were analyzed with X-ray diffraction (XRD) and transmission electron microscopy (TEM), while their spectroscopic and surface properties were characterized by infrared (IR) and X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and 13C cross-polarization magic angle spinning NMR (13C CPMAS NMR). TEM analysis indicated that all the bimetallic clusters prepared are approximately 4-6 nm in size. On the other hand, the results of XRD, XPS, and Fourier transform infrared (FTIR) spectroscopy suggested that the surfaces of the alloy nanoclusters are mostly enriched with the less noble metal copper atoms. This surface enrichment of copper may be attributed to a galvanic exchange process during preparation, and the extent of enrichment is directly related to the copper feed ratio used. Interestingly, DSC studies showed two melting transitions in some of these alloy samples, suggesting different packing behavior of the dodecanethiol chains onto the heterogeneously intercalated silver- and copper-rich surfaces.

  19. Study of highly efficient bimetallic ruthenium tris-bipyridyl ECL labels for coreactant system.

    PubMed

    Sun, Shiguo; Yang, Yang; Liu, Fengyu; Pang, Yi; Fan, Jiangli; Sun, Licheng; Peng, Xiaojun

    2009-12-15

    A series of bimetallic ruthenium complexes [(bpy)(2)Ru(bpy)(CH(2))(n)(bpy)Ru(bpy)(2)](4+) (1, where bpy is 2,2'-bipyridinyl, n = 3, 5, 8) for the coreactant electrochemiluminescence (ECL) system have been synthesized. Their ECL property at different working electrode has been studied in 0.1 M phosphate buffer by using tripropylamine (TPrA) and 2-(dibutylamino) ethanol (DBAE) as the coreactant. The results demonstrate that the ECL intensity depends largely on the length of the saturated carbon chain linkage: the longer is the carbon chain, the higher is the ECL intensity. A remarkable ECL enhancement (up to about 25 times), in comparison with the commonly used metallic [Ru(bpy)(3)](2+), has been observed from 1c (n = 8) at Pt electrode. With 20 mM TPrA, the log of the ECL intensity increases linearly with the log of complex 1c concentrations over the concentration range of 1.0 x 10(-16) to 1.0 x 10(-6) M at glassy carbon electrode. The detection limit is 1.0 x 10(-16) M at a signal-to-noise ratio of 3. This is the highest ECL detection limit for bimetallic system reported until now. The study provides a general methodology to further improve and tune the ECL efficiency by using multimetallic ruthenium complexes.

  20. One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II.

    PubMed

    Luo, Fang; Yang, Die; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2016-02-13

    To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe(2+) and Pd(2+), had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography-Mass Spectrum (HPLC-MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation.

  1. Structural, electronic and adsorption properties of Rh(111)/Mo(110) bimetallic catalyst: A DFT study

    NASA Astrophysics Data System (ADS)

    Palotás, K.; Bakó, I.; Bugyi, L.

    2016-12-01

    Geometric and electronic characterizations of one monolayer rhodium with Nishiyama-Wassermann (NW) structure on Mo(110) substrate have been performed by density functional theory (DFT) calculations. In the NW structure the Rh atoms form a wavy structure propagating along the [001] direction, characterized by an amplitude of 0.26 Å in the [110] direction and by 0.10 Å in the [110] direction of the Mo(110) substrate. Strain and ligand effects operating in the rhodium film are distinguished and found to be manifested in the downward shift of the d-band center of the electron density of states (DOS) by 0.11 eV and 0.18 eV, respectively. The shift in the d-band center of Rh DOS predicts a decrease in the surface reactivity toward CO adsorption, which has been verified by detailed calculations of bond energies of CO located at on-top, bridge and hollow adsorption sites. The CO adsorption energies are decreased by about 35% compared to those reported for pure Rh(111), offering novel catalytic pathways for the molecule. An in-depth analysis of the charge transfer and the partial DOS characters upon CO adsorption on the NW-structured Rh(111)/Mo(110) bimetallic catalyst and on the pure Rh(111) surface sheds light on the bonding mechanism of CO and on the governing factors determining its lowered bond energy on the bimetallic surface.

  2. Modification of TiO2 by Bimetallic Au-Cu Nanoparticles for Wastewater Treatment

    PubMed Central

    Hai, Zibin; Kolli, Nadia EL; Uribe, Daniel Bahena; Beaunier, Patricia; José-Yacaman, Miguel; Vigneron, Jackie; Etcheberry, Arnaud; Sorgues, Sébastien; Colbeau-Justin, Christophe; Chen, Jiafu; Remita, Hynd

    2016-01-01

    Au, Cu and bimetallic Au-Cu nanoparticles were synthesized on the surface of commercial TiO2 compounds (P25) by reduction of the metal precursors with tetrakis (hydroxymethyl) phosphonium chloride (THPC) (0.5 % in weight). The alloyed structure of Au-Cu NPs was confirmed by HAADF-STEM, EDS, HRTEM and XPS techniques. The photocatalytic properties of the modified TiO2 have been studied for phenol photodegradation in aqueous suspensions under UV-visible irradiation. The modification by the metal nanoparticles induces an increase in the photocatalytic activity. The highest photocatalytic activity is obtained with Au-Cu/TiO2 (Au/Cu 1:3). Their electronic properties have been studied by time resolved microwave conductivity (TRMC) to follow the charge-carrier dynamics. TRMC measurements show that the TiO2 modification with Au, Cu and Au-Cu nanoparticles plays a role in charge-carrier separations increasing the activity under UV-light. Indeed, the metal nanoparticles act as a sink for electron, decreasing the charge carrier recombination. The TRMC measurements show also that the bimetallic Au-Cu nanoparticles are more efficient in electron scavenging than the monometallic Au and Cu ones. PMID:27274844

  3. Modification of TiO2 by Bimetallic Au-Cu Nanoparticles for Wastewater Treatment.

    PubMed

    Hai, Zibin; Kolli, Nadia El; Uribe, Daniel Bahena; Beaunier, Patricia; José-Yacaman, Miguel; Vigneron, Jackie; Etcheberry, Arnaud; Sorgues, Sébastien; Colbeau-Justin, Christophe; Chen, Jiafu; Remita, Hynd

    2013-09-28

    Au, Cu and bimetallic Au-Cu nanoparticles were synthesized on the surface of commercial TiO2 compounds (P25) by reduction of the metal precursors with tetrakis (hydroxymethyl) phosphonium chloride (THPC) (0.5 % in weight). The alloyed structure of Au-Cu NPs was confirmed by HAADF-STEM, EDS, HRTEM and XPS techniques. The photocatalytic properties of the modified TiO2 have been studied for phenol photodegradation in aqueous suspensions under UV-visible irradiation. The modification by the metal nanoparticles induces an increase in the photocatalytic activity. The highest photocatalytic activity is obtained with Au-Cu/TiO2 (Au/Cu 1:3). Their electronic properties have been studied by time resolved microwave conductivity (TRMC) to follow the charge-carrier dynamics. TRMC measurements show that the TiO2 modification with Au, Cu and Au-Cu nanoparticles plays a role in charge-carrier separations increasing the activity under UV-light. Indeed, the metal nanoparticles act as a sink for electron, decreasing the charge carrier recombination. The TRMC measurements show also that the bimetallic Au-Cu nanoparticles are more efficient in electron scavenging than the monometallic Au and Cu ones.

  4. Using supported Au nanoparticles as starting material for preparing uniform Au/Pd bimetallic catalysts.

    PubMed

    Villa, Alberto; Wang, Di; Su, Dangsheng; Veith, Gabriel M; Prati, Laura

    2010-03-07

    One of the best methods for producing bulk homogeneous (composition) supported bimetallic AuPd clusters involves the immobilization of a protected Au seed followed by the addition of Pd. This paper investigates the importance of this gold seed in controlling the resulting bimetallic AuPd clusters structures, sizes and catalytic activities by investigating three different gold seeds. Uniform Au-Pd alloy were obtained when a steric/electrostatic protecting group, poly(vinyl alcohol) (PVA), was used to form the gold clusters on activated carbon (AC). In contrast Au/AC precursors prepared using Au nanoparticles with only electrostatic stabilization (tetrakis(hydroxypropyl)phosphonium chloride (THPC)), or no stabilization (magnetron sputtering) produced inhomogeneous alloys and segregation of the gold and palladium. The uniform alloyed catalyst (Pd@Au(PVA)/AC) is the most active and selective catalyst, while the inhomogenous catalysts are less active and selective. Further study of the PVA protected Au clusters revealed that the amount of PVA used is also critical for the preparation of uniform alloyed catalyst, their stability, and their catalytic activity.

  5. Using supported Au nanoparticles as starting material for preparing uniform Au/Pd bimetallic catalysts

    SciTech Connect

    Villa, Alberto; Prati, Laura; Su, Dangshen; Wang, Di; Veith, Gabriel M

    2010-01-01

    One of the best methods for producing bulk homogeneous (composition) supported bimetallic AuPd clusters involves the immobilization of a protected Au seed followed by the addition of Pd. This paper investigates the importance of this gold seed in controlling the resulting bimetallic AuPd clusters structures, sizes and catalytic activities by investigating three different gold seeds. Uniform Au-Pd alloy were obtained when a steric/electrostatic protecting group, poly(vinyl alcohol) (PVA), was used to form the gold clusters on activated carbon (AC). In contrast Au/AC precursors prepared using Au nanoparticles with only electrostatic stabilization (tetrakis(hydroxypropyl)phosphonium chloride (THPC)), or no stabilization (magnetron sputtering) produced inhomogeneous alloys and segregation of the gold and palladium. The uniform alloyed catalyst (Pd{at}Au{sub PVA}/AC) is the most active and selective catalyst, while the inhomogenous catalysts are less active and selective. Further study of the PVA protected Au clusters revealed that the amount of PVA used is also critical for the preparation of uniform alloyed catalyst, their stability, and their catalytic activity.

  6. Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: a mechanistic study.

    PubMed

    Ahmed, Syud M; Poater, Albert; Childers, M Ian; Widger, Peter C B; LaPointe, Anne M; Lobkovsky, Emil B; Coates, Geoffrey W; Cavallo, Luigi

    2013-12-18

    The enantioselective polymerization of propylene oxide (PO) using biaryl-linked bimetallic salen Co catalysts was investigated experimentally and theoretically. Five key aspects of this catalytic system were examined: (1) the structural features of the catalyst, (2) the regio- and stereoselectivity of the chain-growth step, (3) the probable oxidation and electronic state of Co during the polymerization, (4) the role of the cocatalyst, and (5) the mechanism of monomer enchainment. Several important insights were revealed. First, density functional theory (DFT) calculations provided detailed structural information regarding the regio- and stereoselective chain-growth step. Specifically, the absolute stereochemistry of the binaphthol linker determines the enantiomer preference in the polymerization, and the interaction between the salen ligand and the growing polymer chain is a fundamental aspect of enantioselectivity. Second, a new bimetallic catalyst with a conformationally flexible biphenol linker was synthesized and found to enantioselectively polymerize PO, though with lower enantioselectivity than the binaphthol linked catalysts. Third, DFT calculations revealed that the active form of the catalyst has two active exo anionic ligands (chloride or carboxylate) and an endo polymer alkoxide which can ring-open an adjacent cobalt-coordinated epoxide. Fourth, calculations showed that initiation is favored by an endo chloride ligand, while propagation is favored by the presence of two exo carboxylate ligands.

  7. Small bimetallic (Pt/Pd) particles by biosynthesis: transmission electron microscopy and quantum mechanical analysis.

    PubMed

    Herrera-Becerra, R; Zorrilla, C; Canizal, G; Schabes-Retchkiman, P S; Liu, H B; Tavera-Davila, L; Rosano-Ortega, G; Rendon, L; Ascencio, J A

    2009-03-01

    Bimetallic Pd/Pt nanoparticles were synthesized by bio-reduction method. The structural characterizations were performed by high resolution transmission electron microscope and energy dispersive spectroscopy. The size distribution, shapes, structures and elemental distribution were studied for the synthesized samples. Molecular simulation methods based on quantum mechanics have been applied to acquire the further information on their structural stability, electronic properties etc. The results show that the particle size for the pH = 4 was bimodal with an average particle size of 3.2 nm and a variance of 1.8 nm. While for pH is 7 the average is 3.9 nm about the variance increase up to 3.7 nm, and larger particles can be found. By the HREM micrographs, it is identified fcc-like clusters with a few planar defects, which may be pure Pd or Pt, or bimetallic Pd/Pt. Theoretically the most stable configuration corresponds to the Pd18Pt37 eutectic-like structure, which implies a cluster in cluster form.

  8. Active site of bimetallic heterogeneous catalyst by atomic resolution aberration-corrected STEM

    NASA Astrophysics Data System (ADS)

    Hsiao, Chien-Nan; Lin, Chun-Ting

    2015-11-01

    The localized defect of Au-Pd bimetallic heterogeneous nanoparticles catalyst was investigated using HRTEM and aberration-corrected HRSTEM. The phase plates were calculated from the aberration coefficients of the measured probe tableau for various outer tilt angle of the optical axis and the accuracy required for the compensation of the various residual aberration coefficients in order to achieve sub-angstrom resolution with the electron optics system was evaluated up to the fifth order aberrations. It is found that the interplanar spacing of the Au-Pd nanoparticle (1 1 1) planes observed along the [1 1 0] zone axis was approximately 0.24 nm measured by HRTEM. In addition, the HRSTEM HAADF image demonstrated that the twin boundaries on the surfaces of heterogeneous nanoparticles catalysts at atomic scale. These defects might be introduced during the growth to alleviate the internal stress caused by the 4.6% lattice mismatch of Au-Pd bimetallic system. Current research could be applied to the study of active sites in nanocatalysts.

  9. Sulphur adsorption and effects of sulphur poisoning on RhCu bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Foord, J. S.; Reynolds, A. E.

    1985-04-01

    Sulphur adsorption on Cu covered Rh(111) surfaces, prepared as models of "bimetallic cluster" catalysts, was studied and the effects of preadsorbed sulphur on the chemisorption of CO and C 2H 2 on Rh(111)-Cu surfaces examined. In the initial stages of the interaction of sulphur with the metal, strongly bound adsorbate overlayers are formed, while epitaxial sulphide growth takes place at higher sulphur exposures. Sulphur adsorbs indiscriminately on the two components in the bimetallic interface during overlayer formation; preferential formation of Rh 2S 3 is observed, however, at higher sulphur loadings. Sulphur overlayers block the chemisorption of CO and C 2H 2 although blocking is not complete at sulphur concentrations below 8.0 × 10 18 atoms m -2. The extent of adsorption of C 2H 2 falls much more rapidly with increased sulphur coverage than does CO chemisorption, showing that C 2H 2 adsorption requires the larger ensemble size of Rh atoms. Sulphur produces a weakening of the CO adsorption bond by 29 kJ mol -1 but has no effect on the energetics of ethylidyne decomposition.

  10. Microbial synthesis of bimetallic PdPt nanoparticles for catalytic reduction of 4-nitrophenol.

    PubMed

    Tuo, Ya; Liu, Guangfei; Dong, Bin; Yu, Huali; Zhou, Jiti; Wang, Jing; Jin, Ruofei

    2017-02-01

    Bimetallic nanoparticles are generally believed to have improved catalytic activity and stability due to geometric and electronic changes. In this work, biogenic-Pd (bio-Pd), biogenic-Pt (bio-Pt), and biogenic-PdPt (bio-PdPt) nanoparticles were synthesized by Shewanella oneidensis MR-1 in the absence or presence of quinone. Compared with direct microbial reduction process, the addition of anthraquinone-2,6-disulfonate (AQDS) could promote the reduction efficiency of Pd(II) or/and Pt(IV) and result in decrease of particles size. All kinds of nanoparticles could catalyze 4-nitrophenol reduction by NaBH4 and their catalytic activities took the following order: bio-PdPt (AQDS) ∼ bio-PdPt > bio-Pd (AQDS) > bio-Pd > bio-Pt (AQDS) ∼ bio-Pt. Moreover, the bio-PdPt (AQDS) nanoparticles could be reused for 6 cycles. We believe that this simple and efficient biosynthesis approach for synthesizing bimetallic bio-PdPt nanocatalysts is important for preparing active and stable catalysts.

  11. Performance of vertically oriented graphene supported platinum-ruthenium bimetallic catalyst for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Bo, Zheng; Hu, Dan; Kong, Jing; Yan, Jianhua; Cen, Kefa

    2015-01-01

    This work reports the electrocatalytic performance of vertically oriented graphene (VG) supported Pt-Ru bimetallic catalysts toward methanol oxidation reaction (MOR). Dense networks of VG are directly synthesized on carbon paper (CP) via a microwave plamsa-enhanced chemical vapor deposition (PECVD) method. A repeated pulse potentials approach is applied in a conventional three-electrode electrochemical system for the co-electrodeposition of Pt-Ru bimetallic nanoparticles. It is found that, the decoration of VG can simultaneously lead to a ∼3.5 times higher catalyst mass loading and a ∼50% smaller nanoparticle size than the pristine CP counterparts. An optimum Pt molar ratio of 83.4% in the deposits, achieved with a [H2PtCl6]:[RuCl3] of 1:1 in the electrolyte, is clarified with synthetically considering the mass specific activity, CO tolerance, and catalytic stability. According to Tafel analysis and cyclic voltammetry (CV) tests, the Pt-Ru/VG catalyst with the optimized Pt molar ratio can realize a faster methanol dehydrogenation than Pt/VG, and present a significantly enhanced catalytic activity (maximum current density of 339.2 mA mg-1) than those using pristine CP and Vulcan XC-72 as the supports.

  12. Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

    DOE PAGES

    Jia, Lijuan; Yu, Jiangdong; Chen, Yuan; ...

    2017-02-27

    The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively.more » Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.« less

  13. First principles investigations of small bimetallic PdGa clusters as catalysts for hydrogen dissociation

    NASA Astrophysics Data System (ADS)

    Kaul, Indu; Ghosh, Prasenjit

    2017-04-01

    Using first principles density functional theory based calculations, we have studied hydrogen dissociation on sub nanometer bimetallic clusters formed from d-block (Pd) and p-block (Ga) elements in gas phase to explore the feasibility of using them as cheap catalysts for hydrogen dissociation. Our calculations show that the dimers, trimers and tetramers of these clusters are thermodynamically more stable than the pure ones for all Ga concentrations. For a given cluster size, we find that the clusters containing equal amount of Pd and Ga are the most stable ones. In contrast to bulk PdGa, the contribution of Pd-d states to the highest occupied molecular orbitals of the bimetallic clusters are either very small or absent. Study of adsorption of hydrogen molecule on these clusters show that hydrogen binds in an activated form only on the Pd rich clusters. From the calculations of hydrogen dissociation barriers on tetramers of pure Pd, 25% Ga (Pd3Ga) and 50% Ga (Pd2Ga2) we find that Pd3Ga is the most efficient catalyst for hydrogen dissociation with barriers even lower than that on the PdGa surfaces.

  14. Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming.

    PubMed

    Pastor-Pérez, Laura; Merlo, Andrea; Buitrago-Sierra, Robison; Casella, Mónica; Sepúlveda-Escribano, Antonio

    2015-12-01

    A detailed study on the preparation of bimetallic PtSn/C catalysts using surface-controlled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry on Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts' stability when working under more severe reaction conditions.

  15. Stabilization of Au at edges of bimetallic PdAu nanocrystallites.

    PubMed

    Yudanov, Ilya V; Neyman, Konstantin M

    2010-05-21

    Density functional calculations were performed to study the distribution of Au atoms in bimetallic PdAu nanoparticles. A series of Pd(79-n)Au(n) clusters of truncated octahedral shape with different content of Au ranging from n = 1 to 60 was used to model such bimetallic nanosystems. Segregation of Au to the particle surface is found to be thermodynamically favorable. The most stable sites for Au substitution are located at the edges of the PdAu nanoclusters. The stabilization at the edges is rationalized by their higher flexibility for surface relaxation which minimizes the strain induced by larger atomic radius of Au as compared to Pd. This stabilization of Au at the edges indicates the possibility to synthesize PdAu particles with Pd atoms located mainly on the facets, and edges "decorated" by Au atoms. Such nanocrystallites are expected to exhibit peculiar catalytic properties and, being thermodynamically stable, should be prone to retaining their initial shape under catalytic conditions.

  16. Superhydrophobic surface with hierarchical architecture and bimetallic composition for enhanced antibacterial activity.

    PubMed

    Zhang, Mei; Wang, Ping; Sun, Hongyan; Wang, Zuankai

    2014-12-24

    Developing robust antibacterial materials is of importance for a wide range of applications such as in biomedical engineering, environment, and water treatment. Herein we report the development of a novel superhydrophobic surface featured with hierarchical architecture and bimetallic composition that exhibits enhanced antibacterial activity. The surface is created using a facile galvanic replacement reaction followed by a simple thermal oxidation process. Interestingly, we show that the surface's superhydrophobic property naturally allows for a minimal bacterial adhesion in the dry environment, and also can be deactivated in the wet solution to enable the release of biocidal agents. In particular, we demonstrate that the higher solubility nature of the thermal oxides created in the thermal oxidation process, together with the synergistic cooperation of bimetallic composition and hierarchical architecture, allows for the release of metal ions in a sustained and accelerated manner, leading to enhanced antibacterial performance in the wet condition as well. We envision that the ease of fabrication, the versatile functionalities, and the robustness of our surface will make it appealing for broad applications.

  17. Bimetallic oxamato complexes synthesized into mesoporous matrix as precursor to tunable nanosized oxide

    SciTech Connect

    Kalinke, Lucas H.G.; Stumpf, Humberto O.; Mazali, Italo O.; Cangussu, Danielle

    2015-10-15

    Highlights: • The bimetallic oxamato complexes as single-source precursor. • We prepared into a porous silica glass tunable nanosized oxide powders. • X-ray diffraction shows the formation of CeO{sub 2}/CuO and spinel cobaltite. • The different number of IDC allows control of the nanoparticle size. - Abstract: The bimetallic complexes were employed to prepare into a porous silica glass tunable nanosized oxide powders through the single source precursor (SSP) method. These materials were prepared by first anchoring of [Cu(opba)]{sup 2−} [opba = ortho-phenylenebis(oxamato)], second by reaction in situ with second metal [Co(II) or Ce(III)] and followed by a thermal treatment. The different number of impregnation–decomposition cycles (IDC) allows control of the nanoparticle size. X-ray diffraction shows the formation of mixture CeO{sub 2}–CuO and spinel copper cobaltite. Raman spectroscopy confirmed the formation of such phases. Transmission electron microscopy images revealed that spinel cobaltite particles (8 IDC) present a mean size of about 9 nm, whereas for the CeO{sub 2}–CuO phase the particle diameters are 4 nm (2 IDC) and 8 nm (6 IDC). For CeO{sub 2}–CuO the diffuse reflectance spectroscopy indicates a consistent red shift in band gap from 3.41 to 2.87 eV with increasing of particle size due to quantum confinement effect.

  18. Characterization of Na+- beta-Zeolite Supported Pd and Pd Ag Bimetallic Catalysts using EXAFS, TEM and Flow Reactor

    SciTech Connect

    Huang,W.; Lobo, R.; Chen, J.

    2008-01-01

    Flow reactor studies of the selective hydrogenation of acetylene in the presence of ethylene have been performed on Na+ exchanged {beta}-zeolite supported Pd, Ag and PdAg catalysts, as an extension of our previous batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. Results from flow reactor studies show that the PdAg/Na+-{beta}-zeolite bimetallic catalyst has lower activity than Pd/Na+-{beta}-zeolite monometallic catalyst, while Ag/Na+-{beta}-zeolite does not show any activity for acetylene hydrogenation. However, the selectivity for the PdAg bimetallic catalyst is much higher than that for either the Pd catalyst or Ag catalyst. The selectivity to byproduct (ethane) is greatly inhibited on the PdAg bimetallic catalyst as well. The results from the current flow reactor studies confirmed the pervious results from batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. In addition, we used transmission electron microscope (TEM), extended X-ray absorption fine structure (EXAFS), and FTIR of CO adsorption to confirm the formation of Pd-Ag bimetallic alloy in the PdAg/Na+-{beta}-zeolite catalyst.

  19. Effect of mono- and bimetallic nanoparticles Fe, Ni, & Fe/Ni based on carbon nanocomposites on electrocatalytic properties of anodes

    NASA Astrophysics Data System (ADS)

    Ranabhat, K.; Pylinina, A. I.; Skripkin, K. S.; Sofronova, E. A.; Revina, A. A.; Kasatkin, V. E.; Patrikeev, L. N.; Lapshinsky, V. A.

    2016-10-01

    The optical properties of metallic Fe nanoparticles (NPs), Ni NPs and bimetallic Fe/Ni NPs produced under radiolysis in anaerobic condition based on a chemical reduction in the presence of oxygen and quercetin in reversed micellar solutions, and electrokinetic properties of nanoparticles carbon-based nanocomposites were studied. The possibility of the preparation of coating using different nanocomposites with anomalous electrocatalytic is addressed.

  20. Final Technical Report: First Principles Investigations for the Ensemble Effects of PdAu and PtAu Bimetallic Nanocatalysts

    SciTech Connect

    Ruqian Wu

    2012-05-18

    Bimetallic surfaces with tunable chemical properties have attracted broad attention in recent years due to their ample potential for heterogeneous catalysis applications. The local chemical properties of constituents are strongly altered from their parent metals by 'ligand effect', a term encompassing the influences of charge transfer, orbital rehybridization and lattice strain. In comparison to the aforementioned, the 'ensemble effect' associated with particular arrangements of the active constituents have received much less attention, despite their notable importance towards the determination of reactivity and selectivity of bimetallic catalysts. We performed theoretical studies for understanding the ensemble effects on bimetallic catalysis: (i) simulations for the formation of different ensembles on PdAu and PtAu nanoclusters; (ii) studies of the size, shape, and substrate dependence of their electronic properties; and (iii) simulations for model reactions such as CO oxidation, methanol, ethylene and water dehydrogenation on PdAu and PtAu nanoclusters. In close collaboration with leading experimental groups, our theoretical research elucidated the fundamentals of Au based bimetallic nanocatalysts.

  1. Core-shell Rh-Pt nanocubes: A model for studying compressive strain effects in bimetallic nanocatalysts

    NASA Astrophysics Data System (ADS)

    Harak, Ethan William

    Shape-controlled bimetallic nanocatalysts often have increased activities and stabilities over their monometallic counterparts due to surface strain effects and electron transfer between the two metals. Here, we demonstrate that the degree of surface strain can be manipulated in shape-controlled nanocrystals through a bimetallic core shell architecture. This ability is achieved in a model core shell Rh Pt nanocube system through control of shell thickness. An increase in the Pt shell thickness leads to more compressive strain, which can increase the Pt 4f7/2 binding energy by as much as 0.13 eV. This change in electronic structure is correlated with a weakening of surface-adsorbate interactions, which we exploit to reduce catalyst poisoning by CO during formic acid electrooxidation. In fact, by precisely controlling the Pt shell thickness, the maximum current density achieved with Rh Pt nanocubes was 3.5 times greater than that achieved with similarly sized Pt nanocubes, with decreased CO generation as well. This system serves as a model for how bimetallic architectures can be used to manipulate the electronic structure of nanoparticle surfaces for efficient catalysis. The strategy employed here should enable the performance of bimetallic nanomaterials comprised of more cost-effective metals to be enhanced as well.

  2. Asymmetric Synthesis of Ramariolides A and C through Bimetallic Cascade Cyclization and Z-E Isomerization Reaction.

    PubMed

    Pal, Pratik; Nanda, Samik

    2017-03-03

    A short and flexible asymmetric synthesis of ramariolides A and C was accomplished. A bimetallic catalytic system consisting of Pd-Cu-mediated cascade cyclization, unprecedented Z-E isomerization by a Ru-based metathesis catalyst, and late-stage stereoselective epoxidation are the key steps involved in the synthesis.

  3. Kinetically controlled overgrowth of Ag or Au on Pd nanocrystal seeds: from hybrid dimers to nonconcentric and concentric bimetallic nanocrystals.

    PubMed

    Zhu, Cun; Zeng, Jie; Tao, Jing; Johnson, Matthew C; Schmidt-Krey, Ingeborg; Blubaugh, Lynn; Zhu, Yimei; Gu, Zhongze; Xia, Younan

    2012-09-26

    This article describes a systematic study of the nucleation and growth of Ag (and Au) on Pd nanocrystal seeds. By carefully controlling the reaction kinetics, the newly formed Ag atoms could be directed to selectively nucleate and then epitaxially grow on a specific number (ranging from one to six) of the six faces on a cubic Pd seed, leading to the formation of bimetallic nanocrystals with a variety of different structures. In addition to changing the injection rate of precursor, we also systematically investigated other reaction parameters including the capping agent, reductant, and reaction temperature. Our results suggest that the site-selective growth of Ag on cubic Pd seeds could be readily realized by optimizing these reaction parameters. On the basis of the positions of Pd seeds inside the bimetallic nanocrystals as revealed by TEM imaging and elemental mapping, we could identify the exact growth pathways and achieve a clear and thorough understanding of the mechanisms. We have successfully applied the same strategy based on kinetic control to cubic Pd seeds with different sizes and octahedral Pd seeds of one size to generate an array of novel bimetallic nanocrystals with well-controlled structures. With cubic Pd seeds as an example, we have also extended this strategy to the Pd-Au system. We believe this work will provide a promising route to the fabrication of bimetallic nanocrystals with novel structures and properties for applications in plasmonics, catalysis, and other areas.

  4. Dry Reforming of Ethane and Butane with CO2 over PtNi/CeO2 Bimetallic Catalysts

    DOE PAGES

    Yan, Binhang; Yang, Xiaofang; Yao, Siyu; ...

    2016-09-21

    Dry reforming is a potential process to convert CO2 and light alkanes into syngas (H2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce4+ to Ce3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS), X-ray Diffraction (XRD) andmore » X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.« less

  5. Action of bimetallic nanocatalysts under reaction conditions and during catalysis: evolution of chemistry from high vacuum conditions to reaction conditions.

    PubMed

    Tao, Franklin Feng; Zhang, Shiran; Nguyen, Luan; Zhang, Xueqiang

    2012-12-21

    Bimetallic catalysts are one of the main categories of metal catalysts due to the tunability of electronic and geometric structures through alloying a second metal. The integration of a second metal creates a vast number of possibilities for varying the surface structure and composition of metal catalysts toward designing new catalysts. It is well acknowledged that the surface composition, atomic arrangement, and electronic state of bimetallic catalysts could be different from those before a chemical reaction or catalysis based on ex situ studies. Thanks to advances in electron-based surface analytical techniques, the surface chemistry and structure of bimetallic nanoparticles can be characterized under reaction conditions and during catalysis using ambient pressure analytical techniques including ambient pressure XPS, ambient pressure STM, X-ray absorption spectroscopy and others. These ambient pressure studies revealed various restructurings in the composition and arrangement of atoms in the surface region of catalysts under reaction conditions or during catalysis compared to that before reaction. These restructurings are driven by thermodynamic and kinetic factors. The surface energy of the constituent metals and adsorption energy of reactant molecules or dissociated species on a metal component are two main factors from the point of view of thermodynamics. Correlations between the authentic surface structure and chemistry of catalysts during catalysis and simultaneous catalytic performance were built for understanding catalytic mechanisms of bimetallic catalysts toward designing new catalysts with high activity, selectivity, and durability.

  6. Alternative nanostructures for thermophones

    NASA Astrophysics Data System (ADS)

    Mayo, Nathanael; Aliev, Ali; Baughman, Ray

    2015-03-01

    There is a large promise for thermophones in high power sonar arrays, flexible loudspeakers, and noise cancellation devices. So far, freestanding aerogel-like carbon nanotube sheets demonstrate the best performance as a thermoacoustic heat source. However, the limited accessibility of large size freestanding carbon nanotube sheets and other even more exotic materials published recently, hampers the field. We present here new alternative materials for a thermoacoustic heat source with high energy conversion efficiency, additional functionalities, environmentally friendly and cost effective production technologies. We discuss the thermoacoustic performance of alternative nanoscale materials and compare their spectral and power dependencies of sound pressure in air. The study presented here focuses on engineering thermal gradients in the vicinity of nanostructures and subsequent heat dissipation processes from the interior of encapsulated thermoacoustic projectors. Applications of thermoacoustic projectors for high power SONAR arrays, sound cancellation, and optimal thermal design, regarding enhanced energy conversion efficiency, are discussed.

  7. Repairable, nanostructured biomimetic hydrogels

    NASA Astrophysics Data System (ADS)

    Firestone, M.; Brombosz, S.; Grubjesic, S.

    2013-03-01

    Proteins facilitate many key cellular processes, including signal recognition and energy transduction. The ability to harness this evolutionarily-optimized functionality could lead to the development of protein-based systems useful for advancing alternative energy storage and conversion. The future of protein-based, however, requires the development of materials that will stabilize, order and control the activity of the proteins. Recently we have developed a synthetic approach for the preparation of a durable biomimetic chemical hydrogel that can be reversibly swollen in water. The matrix has proven ideal for the stable encapsulation of both water- and membrane-soluble proteins. The material is composed of an aqueous dispersion of a diacrylate end-derivatized PEO-PPO-PEO macromer, a saturated phospholipid and a zwitterionic co-surfactant that self-assembles into a nanostructured physical gel at room temperature as determined by X-ray scattering. The addition of a water soluble PEGDA co-monomer and photoinitator does not alter the self-assembled structure and UV irradiation serves to crosslink the acrylate end groups on the macromer with the PEGDA forming a network within the aqueous domains as determined by FT-IR. More recently we have begun to incorporate reversible crosslinks employing Diels-Alder chemistry, allowing for the extraction and replacement of inactive proteins. The ability to replenish the materials with active, non-denatured forms of protein is an important step in advancing these materials for use in nanostructured devices This work was supported by the Office of Basic Energy Sciences, Division of Materials Sciences, USDoE under Contract No. DE-AC02-06CH11357.

  8. Nanostructured Materials for Renewable Energy

    SciTech Connect

    2009-11-01

    This factsheet describes a research project whose overall objective is to advance the fundamental understanding of novel photoelectronic organic device structures integrated with inorganic nanostructures, while also expanding the general field of nanomaterials for renewable energy devices and systems.

  9. Microscopic characterization of peptide nanostructures.

    PubMed

    Mammadov, Rashad; Tekinay, Ayse B; Dana, Aykutlu; Guler, Mustafa O

    2012-02-01

    Peptide-based nanomaterials have been utilized for various applications from regenerative medicine to electronics since they provide several advantages including easy synthesis methods, numerous routes for functionalization and biomimicry of secondary structures of proteins which leads to design of self-assembling peptide molecules to form nanostructures. Microscopic characterization at nanoscale is critical to understand processes directing peptide molecules to self-assemble and identify structure-function relationship of the nanostructures. Here, fundamental studies in microscopic characterization of peptide nanostructures are discussed to provide insights in widely used microscopy tools. In this review, we will encompass characterization studies of peptide nanostructures with modern microscopes, such as TEM, SEM, AFM, and advanced optical microscopy techniques. We will also mention specimen preparation methods and describe interpretation of the images.

  10. NiW and NiRu Bimetallic Catalysts for Ethylene Steam Reforming: Alternative Mechanisms for Sulfur Resistance

    SciTech Connect

    Rangan, M.; Yung, M. M.; Medlin, J. W.

    2012-06-01

    Previous investigations of Ni-based catalysts for the steam reforming of hydrocarbons have indicated that the addition of a second metal can reduce the effects of sulfur poisoning. Two systems that have previously shown promise for such applications, NiW and NiRu, are considered here for the steam reforming of ethylene, a key component of biomass derived tars. Monometallic and bimetallic Al{sub 2}O{sub 3}-supported Ni and W catalysts were employed for ethylene steam reforming in the presence and absence of sulfur. The NiW catalysts were less active than Ni in the absence of sulfur, but were more active in the presence of 50 ppm H{sub 2}S. The mechanism for the W-induced improvements in sulfur resistance appears to be different from that for Ru in NiRu. To probe reasons for the sulfur resistance of NiRu, the adsorption of S and C{sub 2}H{sub 4} on several bimetallic NiRu alloy surfaces ranging from 11 to 33 % Ru was studied using density functional theory (DFT). The DFT studies reveal that sulfur adsorption is generally favored on hollow sites containing Ru. Ethylene preferentially adsorbs atop the Ru atom in all the NiRu (111) alloys investigated. By comparing trends across the various bimetallic models considered, sulfur adsorption was observed to be correlated with the density of occupied states near the Fermi level while C{sub 2}H{sub 4} adsorption was correlated with the number of unoccupied states in the d-band. The diverging mechanisms for S and C{sub 2}H{sub 4} adsorption allow for bimetallic surfaces such as NiRu that enhance ethylene binding without accompanying increases in sulfur binding energy. In contrast, bimetallics such as NiSn and NiW appear to decrease the affinity of the surface for both the reagent and the poison.

  11. Characterization of Nanostructured Polymer Films

    DTIC Science & Technology

    2014-12-23

    of the film for complete polymer chain relaxation, including relaxation of surface features . The presence of intact surface globules at a substrate...AFRL-OSR-VA-TR-2015-0059 Characterization of Nanostructured Polymer Films RODNEY PRIESTLEY TRUSTEES OF PRINCETON UNIVERSITY Final Report 12/23/2014...Report 3. DATES COVERED (From - To) 06/01/2012-08/31/2014 4. TITLE AND SUBTITLE Characterization of Nanostructured Polymer Films 5a. CONTRACT

  12. Nanostructure-induced DNA condensation

    NASA Astrophysics Data System (ADS)

    Zhou, Ting; Llizo, Axel; Wang, Chen; Xu, Guiying; Yang, Yanlian

    2013-08-01

    The control of the DNA condensation process is essential for compaction of DNA in chromatin, as well as for biological applications such as nonviral gene therapy. This review endeavours to reflect the progress of investigations on DNA condensation effects of nanostructure-based condensing agents (such as nanoparticles, nanotubes, cationic polymer and peptide agents) observed by using atomic force microscopy (AFM) and other techniques. The environmental effects on structural characteristics of nanostructure-induced DNA condensates are also discussed.

  13. Catalytic Sorption of (Chloro)Benzene and Napthalene in Aqueous Solutions by Granular Activated Carbon Supported Bimetallic Iron and Palladium Nanoparticles

    EPA Science Inventory

    Adsorption of benzene, chlorobenzene, and naphthalene on commercially available granular activated carbon (GAC) and bimetallic nanoparticle (Fe/Pd) loaded GAC was investigated for the potential use in active capping of contaminated sediments. Freundlich and Langmuir linearizatio...

  14. CATALYSIS SCIENCE INITIATIVE: From First Principles Design to Realization of Bimetallic Catalysts for Enhanced Selectivity

    SciTech Connect

    MAVRIKAKIS, MANOS DUMESIC, JAMES A.

    2007-05-03

    In this project, we have integrated state-of-the-art Density Functional Theory (DFT) models of heterogeneous catalytic processes with high-throughput screening of bimetallic catalytic candidates for important industrial problems. We have studied a new class of alloys characterized by a surface composition different from the bulk composition, and investigated their stability and activity for the water-gas shift reaction and the oxygen reduction reaction. The former reaction is an essential part of hydrogen production; the latter is the rate-limiting step in low temperature H2 fuel cells. We have identified alloys that have remarkable stability and activity, while having a much lower material cost for both of these reactions. Using this knowledge of bimetallic interactions, we have also made progress in the industrially relevant areas of carbohydrate reforming and conversion of biomass to liquid alkanes. One aspect of this work is the conversion of glycerol (a byproduct of biodiesel production) to synthesis gas. We have developed a bifunctional supported Pt catalyst that can cleave the carbon-carbon bond while also performing the water-gas shift reaction, which allows us to better control the H2:CO ratio. Knowledge gained from the theoretical metal-metal interactions was used to develop bimetallic catalysts that perform this reaction at low temperature, allowing for an efficient coupling of this endothermic reaction with other reactions, such as Fischer-Tropsch or methanol synthesis. In our work on liquid alkane production from biomass, we have studied deactivation and selectivity in these areas as a function of metal-support interactions and reaction conditions, with an emphasis on the bifunctionality of the catalysts studied. We have identified a stable, active catalyst for this process, where the selectivity and yield can be controlled by the reaction conditions. While complete rational design of catalysts is still elusive, this work demonstrates the power of

  15. Strategies for designing supported gold-palladium bimetallic catalysts for the direct synthesis of hydrogen peroxide.

    PubMed

    Edwards, Jennifer K; Freakley, Simon J; Carley, Albert F; Kiely, Christopher J; Hutchings, Graham J

    2014-03-18

    Hydrogen peroxide is a widely used chemical but is not very efficient to make in smaller than industrial scale. It is an important commodity chemical used for bleaching, disinfection, and chemical manufacture. At present, manufacturers use an indirect process in which anthraquinones are sequentially hydrogenated and oxidized in a manner that hydrogen and oxygen are never mixed. However, this process is only economic at a very large scale producing a concentrated product. For many years, the identification of a direct process has been a research goal because it could operate at the point of need, producing hydrogen peroxide at the required concentration for its applications. Research on this topic has been ongoing for about 100 years. Until the last 10 years, catalyst design was solely directed at using supported palladium nanoparticles. These catalysts require the use of bromide and acid to arrest peroxide decomposition, since palladium is a very active catalyst for hydrogen peroxide hydrogenation. Recently, chemists have shown that supported gold nanoparticles are active when gold is alloyed with palladium because this leads to a significant synergistic enhancement in activity and importantly selectivity. Crucially, bimetallic gold-based catalysts do not require the addition of bromide and acids, but with carbon dioxide as a diluent its solubility in the reaction media acts as an in situ acid promoter, which represents a greener approach for peroxide synthesis. The gold catalysts can operate under intrinsically safe conditions using dilute hydrogen and oxygen, yet these catalysts are so active that they can generate peroxide at commercially significant rates. The major problem associated with the direct synthesis of hydrogen peroxide concerns the selectivity of hydrogen usage, since in the indirect process this factor has been finely tuned over decades of operation. In this Account, we discuss how the gold-palladium bimetallic catalysts have active sites for the

  16. Kinetics and mechanism of the liquid-phase oxidation of cyclohexene. IV. Decomposition of cyclohexenyl hydroperoxide in the presence of bimetallic catalysts

    SciTech Connect

    Baevskii, M.Yu.; Litvintsev, I.Yu.; Sapunov, V.N.

    1988-11-01

    The kinetic principles of the decomposition of cyclohexenyl hydroperoxide in cyclohexene solution in homogeneous catalysis by vanadium-containing bimetallic systems were investigated. For Co-V and Pb-V, the formation of complexes with low activity in catalysis was demonstrated by kinetic and spectral methods. A mathematical model was obtained for the process, adequately describing the conversions of cyclohexenyl hydroperoxide in the presence of bimetallic systems.

  17. Chemically enabled nanostructure fabrication

    NASA Astrophysics Data System (ADS)

    Huo, Fengwei

    The first part of the dissertation explored ways of chemically synthesizing new nanoparticles and biologically guided assembly of nanoparticle building blocks. Chapter two focuses on synthesizing three-layer composite magnetic nanoparticles with a gold shell which can be easily functionalized with other biomolecules. The three-layer magnetic nanoparticles, when functionalized with oligonucleotides, exhibit the surface chemistry, optical properties, and cooperative DNA binding properties of gold nanoparticle probes, while maintaining the magnetic properties of the Fe3O4 inner shell. Chapter three describes a new method for synthesizing nanoparticles asymmetrically functionalized with oligonucleotides and the use of these novel building blocks to create satellite structures. This synthetic capability allows one to introduce valency into such structures and then use that valency to direct particle assembly events. The second part of the thesis explored approaches of nanostructure fabrication on substrates. Chapter four focuses on the development of a new scanning probe contact printing method, polymer pen lithography (PPL), which combines the advantages of muCp and DPN to achieve high-throughput, flexible molecular printing. PPL uses a soft elastomeric tip array, rather than tips mounted on individual cantilevers, to deliver inks to a surface in a "direct write" manner. Arrays with as many as ˜11 million pyramid-shaped pens can be brought into contact with substrates and readily leveled optically in order to insure uniform pattern development. Chapter five describes gel pen lithography, which uses a gel to fabricate pen array. Gel pen lithography is a low-cost, high-throughput nanolithography method especially useful for biomaterials patterning and aqueous solution patterning which makes it a supplement to DPN and PPL. Chapter 6 shows a novel form of optical nanolithography, Beam Pen Lithography (BPL), which uses an array of NSOM pens to do nanoscale optical

  18. Phonon engineering for nanostructures.

    SciTech Connect

    Aubry, Sylvie; Friedmann, Thomas Aquinas; Sullivan, John Patrick; Peebles, Diane Elaine; Hurley, David H.; Shinde, Subhash L.; Piekos, Edward Stanley; Emerson, John Allen

    2010-01-01

    Understanding the physics of phonon transport at small length scales is increasingly important for basic research in nanoelectronics, optoelectronics, nanomechanics, and thermoelectrics. We conducted several studies to develop an understanding of phonon behavior in very small structures. This report describes the modeling, experimental, and fabrication activities used to explore phonon transport across and along material interfaces and through nanopatterned structures. Toward the understanding of phonon transport across interfaces, we computed the Kapitza conductance for {Sigma}29(001) and {Sigma}3(111) interfaces in silicon, fabricated the interfaces in single-crystal silicon substrates, and used picosecond laser pulses to image the thermal waves crossing the interfaces. Toward the understanding of phonon transport along interfaces, we designed and fabricated a unique differential test structure that can measure the proportion of specular to diffuse thermal phonon scattering from silicon surfaces. Phonon-scale simulation of the test ligaments, as well as continuum scale modeling of the complete experiment, confirmed its sensitivity to surface scattering. To further our understanding of phonon transport through nanostructures, we fabricated microscale-patterned structures in diamond thin films.

  19. Ultrahard magnetic nanostructures

    NASA Astrophysics Data System (ADS)

    Sahota, P. K.; Liu, Y.; Skomski, R.; Manchanda, P.; Zhang, R.; Franchin, M.; Fangohr, H.; Hadjipanayis, G. C.; Kashyap, A.; Sellmyer, D. J.

    2012-04-01

    The performance of hard-magnetic nanostructures is investigated by analyzing the size and geometry dependence of thin-film hysteresis loops. Compared to bulk magnets, weight and volume are much less important, but we find that the energy product remains the main figure of merit down to very small features sizes. However, hysteresis loops are much easier to control on small length scales, as epitomized by Fe-Co-Pt thin films with magnetizations of up to 1.78 T and coercivities of up to 2.52 T. Our numerical and analytical calculations show that the feature size and geometry have a big effect on the hysteresis loop. Layered soft regions, especially if they have a free surface, are more harmful to coercivity and energy product than spherical inclusions. In hard-soft nanocomposites, an additional complication is provided by the physical properties of the hard phases. For a given soft phase, the performance of a hard-soft composite is determined by the parameter (Ms - Mh)/Kh.

  20. Nanostructures in photovoltaics.

    PubMed

    Catchpole, Kylie R

    2006-12-15

    The world has recently been waking up to the urgent need to move away from fossil fuels and towards a low-carbon economy. To achieve this, we need a way of producing electricity that is efficient, widely applicable and cheap. At the same time, there has recently been an appreciation of the tremendous scope for making entirely new types of devices, and even seeing new physics, by structuring matter at the nanoscale. Furthermore, the occurrence of self-assembly in nature suggests that a range of types of nanoscale structures could be made simply and cheaply. The application of nanostructures to photovoltaics combines a field of almost limitless possibilities with a problem of vital urgency. In this paper, some of the newer ideas emerging from this trend are described, along with how they challenge our ideas on what a solar cell looks like. We are at the beginning of a time of radically rethinking the design of the solar cell, which may lead to the exploitation of completely new physical ideas in achieving a sustainable energy future.

  1. Emissive cyanide-bridged bimetallic compounds as building blocks for polymeric antennae.

    PubMed

    Cadranel, Alejandro; Aramburu Trošelj, Bruno M; Yamazaki, Shiori; Alborés, Pablo; Kleiman, Valeria D; Baraldo, Luis M

    2013-12-28

    A series of cyanide-bridged bimetallic compounds of the general formula [Ru(L)(bpy)(μ-NC)(M)](2-/-/2+) (L = tpy, 2,2'-6',2''-terpyridine, or tpm, tris(1-pyrazolyl)methane, bpy = 2,2'-bipyridine, M = Ru(II)(CN)5, Os(III)(CN)5, Os(II)(CN)5, Ru(II)(py)4(CN), py = pyridine) have been synthesized and fully characterized. Most of them present MLCT emission (λ = 690-730 nm, Φ = 10(-3)-10(-4)) and their photophysical properties resemble the ones of the respective mononuclear Ru(L)(bpy) species. The exception is when M is Os(III)(CN)5, where an intramolecular electron transfer quenching mechanism is proposed. The conditions that should be met for avoiding the reductive or oxidative quenching of the excited state are also discussed.

  2. Bimetallic octahedral ruthenium-nickel carbido cluster complexes. Synthesis and structural characterization.

    PubMed

    Saha, Sumit; Zhu, Lei; Captain, Burjor

    2013-03-04

    The reaction of Ru5(CO)15(μ5-C) with Ni(COD)2 in acetonitrile at 80 °C affords the bimetallic octahedral ruthenium-nickel cluster complex Ru5Ni(NCMe)(CO)15(μ6-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH3 to yield Ru5Ni(CO)16(μ6-C), 4, and Ru5Ni(NH3)(CO)15(μ6-C), 5, respectively. Photolysis of compound 3 in benzene and toluene solvent yielded the η(6)-coordinated benzene and toluene Ru5Ni carbido cluster complexes Ru5Ni(CO)13(η(6)-C6H6)(μ6-C), 6, and Ru5Ni(CO)13(η(6)-C7H8)(μ6-C), 7, respectively. All five new compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  3. Development of bi-metallic Fe-Bi nanocomposites: synthesis and characterization.

    PubMed

    Mattei, J G; Pelletier, F; Ciuculescu, D; Lecante, P; Amiens, C; Casanove, M J

    2012-11-01

    We investigate the formation of bi-metallic particles in the Fe-Bi system, well known as totally immiscible in the bulk, using a large combination of structural and element-sensitive techniques, well-adapted to the nanoscale. The synthesis approach makes use of the kinetics of decomposition of the different precursors to achieve a controlled sequential growth of the different elements. Different ligands have also been used in order to limit the size and ensure dispersion of the synthesized particles. Our results give evidence for the presence of body-centered cubic ferromagnetic iron nanograins together with larger bismuth crystallites. Interestingly, while the iron particles remain very small, the resistance to oxidation of the Fe-Bi nanocomposites highly depends on the stabilizing ligand used in the synthesis. The presence of both metals, Fe and Bi, in a single cluster has been clearly revealed in the oxidation resistant composite synthesized using the HMDS ligand.

  4. Synthesis of homogeneous Pt-bimetallic nanoparticles as highly efficient electrocatalysts.

    SciTech Connect

    Wang, C.; Chi, M.; Li, D.; van der Vliet, D.; Wang, G.; Lin, Q.; Mitchell, J.; More, K. L.; Markovic, N. M.; Stamenkovic, V. R.

    2011-01-01

    Alloying has shown enormous potential for tailoring the atomic and electronic structures, and improving the performance of catalytic materials. Systematic studies of alloy catalysts are, however, often compromised by inhomogeneous distribution of alloying components. Here we introduce a general approach for the synthesis of monodispersed and highly homogeneous Pt-bimetallic alloy nanocatalysts. Pt{sub 3}M (where M = Fe, Ni, or Co) nanoparticles were prepared by an organic solvothermal method and then supported on high surface area carbon. These catalysts attained a homogeneous distribution of elements, as demonstrated by atomic-scale elemental analysis using scanning transmission electron microscopy. They also exhibited high catalytic activities for the oxygen reduction reaction (ORR), with improvement factors of 2-3 versus conventional Pt/carbon catalysts. The measured ORR catalytic activities for Pt{sub 3}M nanocatalysts validated the volcano curve established on extended surfaces, with Pt{sub 3}Co being the most active alloy.

  5. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  6. Tunability of the Adsorbate Binding on Bimetallic Alloy Nanoparticles for the Optimization of Catalytic Hydrogenation.

    PubMed

    Luo, Long; Duan, Zhiyao; Li, Hao; Kim, Joohoon; Henkelman, Graeme; Crooks, Richard M

    2017-04-07

    In this paper, we show that PtAu and PdAu random alloy dendrimer-encapsulated nanoparticles with an average size of ∼1.6 nm have different catalytic activity trends for allyl alcohol hydrogenation. Specifically, PtAu nanoparticles exhibit a linear increase in activity with increasing Pt content, whereas PdAu dendrimer-encapsulated nanoparticles show a maximum activity at a Pd content of ∼60%. Both experimental and theoretical results suggest that this contrasting behavior is caused by differences in the strength of H binding on the PtAu and PdAu alloy surfaces. The results have significant implications for predicting the catalytic performance of bimetallic nanoparticles on the basis of density functional theory calculations.

  7. Intrinsic magnetic properties of bimetallic nanoparticles elaborated by cluster beam deposition.

    PubMed

    Dupuis, V; Khadra, G; Hillion, A; Tamion, A; Tuaillon-Combes, J; Bardotti, L; Tournus, F

    2015-11-14

    In this paper, we present some specific chemical and magnetic order obtained very recently on characteristic bimetallic nanoalloys prepared by mass-selected Low Energy Cluster Beam Deposition (LECBD). We study how the competition between d-atom hybridization, complex structure, morphology and chemical affinity affects their intrinsic magnetic properties at the nanoscale. The structural and magnetic properties of these nanoalloys were investigated using various experimental techniques that include High Resolution Transmission Electron Microscopy (HRTEM), Superconducting Quantum Interference Device (SQUID) magnetometry, as well as synchrotron techniques such as Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Magnetic Circular Dichroism (XMCD). Depending on the chemical nature of the nanoalloys we observe different magnetic responses compared to their bulk counterparts. In particular, we show how specific relaxation in nanoalloys impacts their magnetic anisotropy; and how finite size effects (size reduction) inversely enhance their magnetic moment.

  8. Bimetallic alloys in action: dynamic atomistic motifs for electrochemistry and catalysis.

    PubMed

    Mueller, Jonathan E; Krtil, Petr; Kibler, Ludwig A; Jacob, Timo

    2014-08-07

    Bimetallic alloys show great promise for applications in a wide range of technologies related to electrochemistry and heterogeneous catalysis. The alloyed nature of these materials supports the existence of surface phenomena and structural motifs not present in single-component materials. These novel features result in electrochemical and catalytic behaviors, requiring entirely new categories of explanations. In this perspective concrete examples are used to illustrate several of these chemical and structural features, which are unique to multi-component metal surfaces. The influence of the surface's structure and surroundings (e.g. adsorbates) on each other provides a common thread, with the emergence of dynamic surfaces as its terminus. In considering three model systems (PtRu, PtNi and AuPd), we discuss not only a selection of surface phenomena relevant to each, but also the implications of these alloy-related behaviors for the electrochemical and catalytic properties of each surface.

  9. Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

    NASA Astrophysics Data System (ADS)

    Han, Lili; Meng, Qingping; Wang, Deli; Zhu, Yimei; Wang, Jie; Du, Xiwen; Stach, Eric A.; Xin, Huolin L.

    2016-12-01

    An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. This work characterizes the pathways that can control the morphology in binary oxide materials.

  10. Catalytic asymmetric synthesis of 3-aminooxindoles: enantiofacial selectivity switch in bimetallic vs monometallic Schiff base catalysis.

    PubMed

    Mouri, Shinsuke; Chen, Zhihua; Mitsunuma, Harunobu; Furutachi, Makoto; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-02-03

    A highly enantioselective catalytic asymmetric access to 3-aminooxindoles with a tetrasubstituted carbon stereocenter is described. 1-2 mol % of homobimetallic (R)-Ni(2)-Schiff base 1 catalyzed the asymmetric amination of 3-substituted oxindoles with azodicarboxylates to give (R)-products in 99-89% yield and 99-87% ee. Reversal of enantiofacial selectivity was observed between bimetallic and monometallic Schiff base complexes, and monometallic (R)-Ni-Schiff base 2c gave (S)-products in 98-80% ee. Transformation of the products into an optically active oxindole with a spiro-beta-lactam unit and a known key intermediate for AG-041R synthesis is also described.

  11. One-component bimetallic aluminium(salen)-based catalysts for cyclic carbonate synthesis and their immobilization.

    PubMed

    Meléndez, Jaisiel; North, Michael; Villuendas, Pedro; Young, Carl

    2011-04-21

    The development of one-component, bimetallic μ-oxoaluminium(salen) complexes as highly active catalysts for the synthesis of cyclic carbonates from terminal epoxides is described. The resulting homogeneous catalysts are used in batch reactions at room temperature and one atmosphere pressure. The catalysts have also been immobilized onto various support materials and used in either batch reactions or gas-phase flow reactions with ethylene and propylene oxides. Catalyst lifetime, deactivation and reactivation have been studied in both batch and flow reactions, and it has been shown that of the impurities present in power station flue gas, only sulfur trioxide deactivates the catalyst and at the concentrations of sulfur trioxide present in flue gas, this deactivation would require more than one years exposure of the catalyst to flue gas.

  12. Glycerol conversion into value added chemicals over bimetallic catalysts in supercritical carbon dioxide

    NASA Astrophysics Data System (ADS)

    Hidayati, Luthfiana N.; Sudiyarmanto, Adilina, Indri B.

    2017-01-01

    Development of alternative energy from biomass encourage the experiments and production of biodiesel lately. Biodiesel industries widely expand because biodiesel as substitute of fossil fuel recognized as promising renewable energy. Glycerol is a byproduct of biodiesel production, which is resulted 10% wt average every production. Meanwhile, carbon dioxide is a gas that is very abundant amount in the atmosphere. Glycerol and carbon dioxide can be regarded as waste, possibly will produce value-added chemical compounds through chemically treated. In this preliminary study, conversion of glycerol and carbon dioxide using bimetallic catalyst Ni-Sn with various catalyst supports : MgO, γ-Al2O3, and hydrotalcite. Catalysts which have been prepared, then physically characterized by XRD, surface area and porosity analysis, and thermal gravity analysis. Catalytic test performance using supercritical carbon dioxide conditions. Furthermore, the products were analyzed by GC. The final product mostly contained of propylene glycol and glycerol carbonate.

  13. Study to reduce the cost of bimetallic boiler tubes. Final report

    SciTech Connect

    Sponseller, D.L.

    1994-06-01

    This report describes a new method of producing low-alloy steel boiler tubes, clad with stainless steel. In this method the two metals are united directly in the casting stage by centrifugal casting; the hollow bimetallic casting is then cut into billets that are hot extruded. By this method, high-quality clad tubes can be produced at markedly lower cost than by the conventional method of producing clad tubes. This brings the cost down to a level where clad tubes can be considered for applications, such as the following, in U.S. electric utility boilers: (1) High-corrosion areas of existing coal-fired boilers, in both steam-generating tubes and superheaters. (2) Future boilers designed to achieve higher efficiency levels (i.e., ultra supercritical boilers operating at higher pressures and temperatures). (3) The steam-generating tubes of Syngas coolers of integrated coal gasification/electric power generating plants.

  14. Preparation and characterization of platinum-ruthenium bimetallic nanoparticles using reverse microemulsions for fuel cell catalyst.

    PubMed

    Kim, Taeyoon; Kobayashi, Koichi; Nagai, Masayuki

    2007-01-01

    Platinum-ruthenium bimetallic nanoparticles are prepared by chemical reduction using sodium borohydride in reverse microemulsions of water/isooctane/Igepal CA-630/2-propanol for fuel cell catalysts. The prepared nanoparticles are characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and energy-dispersive X-ray analysis. The average size and morphology of nanoparticles are dependent on the water volume fraction in reverse microemulsion system in the range of ca. 2-4 nm. The morphology of particles is related with the percolation behavior of water droplets in reverse microemulsions. By the pretreatment of water phase using a hydrochloric acid, the particles of a homogeneous solid solution state can be obtained. The CO stripping cyclovoltammetry and the electrochemical measurements compared with commercial catalyst show that the prepared particles have a high electrochemically active surface area and a stable and high catalytic activity for reformate gas oxidation.

  15. FORMATION MECHANISM FOR THE NANOSCALE AMORPHOUS INTERFACE IN PULSE-WELDED AL/FE BIMETALLIC SYSTEM

    SciTech Connect

    Li, Jingjing; Yu, Qian; Zhang, Zijiao; Xu, Wei; Sun, Xin

    2016-05-20

    Pulse or impact welding traditionally has been referred to as “solid-state” welding. By integrating advanced interface characterizations and diffusion calculations, we report that the nanoscale amorphous interface in the pulse-welded Al/Fe bimetallic system is formed by rapid heating and melting of a thin Al layer at the interface, diffusion of iron atoms in the liquid aluminum, and subsequent rapid quenching with diffused iron atoms in solution. This finding challenges the commonly held belief regarding the solid-state nature of the impact-based welding process for dissimilar metals. Elongated ultra-fine grains with high dislocation density and ultra-fine equiaxed grains also are observed in the weld interface vicinity on the steel and aluminum sides, respectively, which further confirms that melting and the resulted recrystallization occurred on the aluminum side of the interface.

  16. Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

    PubMed Central

    Han, Lili; Meng, Qingping; Wang, Deli; Zhu, Yimei; Wang, Jie; Du, Xiwen; Stach, Eric A.; Xin, Huolin L.

    2016-01-01

    An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. This work characterizes the pathways that can control the morphology in binary oxide materials. PMID:27928998

  17. Nickel-cobalt bimetallic anode catalysts for direct urea fuel cell.

    PubMed

    Xu, Wei; Zhang, Huimin; Li, Gang; Wu, Zucheng

    2014-08-29

    Nickel is an ideal non-noble metal anode catalyst for direct urea fuel cell (DUFC) due to its high activity. However, there exists a large overpotential toward urea electrooxidation. Herein, NiCo/C bimetallic nanoparticles were prepared with various Co contents (0, 10, 20, 30 and 40 wt%) to improve the activity. The best Co ratio was 10% in the aspect of cell performance, with a maximum power density of 1.57 mW cm(-2) when 0.33 M urea was used as fuel, O2 as oxidant at 60 °C. The effects of temperature and urea concentration on DUFC performance were investigated. Besides, direct urine fuel cell reaches a maximum power density of 0.19 mW cm(-2) with an open circuit voltage of 0.38 V at 60 °C.

  18. Characterization and reactivity of Pd Pt bimetallic supported catalysts obtained by laser vaporization of bulk alloy

    NASA Astrophysics Data System (ADS)

    Rousset, J. L.; Cadete Santos Aires, F. J.; Bornette, F.; Cattenot, M.; Pellarin, M.; Stievano, L.; Renouprez, A. J.

    2000-09-01

    Bimetallic Pd-Pt clusters produced by laser vaporization of bulk alloy have been deposited on high surface alumina. Energy dispersive X-ray (EDX) analysis and transmission electron microscopy (TEM) show that they have a perfectly well-defined stoichiometry and a narrow range of size. Therefore, they constitute ideal systems to investigate alloying effects towards reactivity. Pd-Pt alloys are already known for their applications in the hydrogenation of unsaturated hydrocarbons, especially aromatics, because this system is highly resistant to sulfur and nitrogen poisoning. In this context, the catalytic properties of this system have been investigated in the hydrogenation of tetralin in the presence of hydrogen sulfide. Preliminary results show that this model catalyst is more sulfur-resistant than each of the pure supported metals prepared by chemical methods.

  19. Bi-Metallic Composite Structures With Designed Internal Residual Stress Field

    NASA Technical Reports Server (NTRS)

    Brice, Craig A.

    2014-01-01

    Shape memory alloys (SMA) have a unique ability to recover small amounts of plastic strain through a temperature induced phase change. For these materials, mechanical displacement can be accomplished by heating the structure to induce a phase change, through which some of the plastic strain previously introduced to the structure can be reversed. This paper introduces a concept whereby an SMA phase is incorporated into a conventional alloy matrix in a co-continuous reticulated arrangement forming a bi-metallic composite structure. Through memory activation of the mechanically constrained SMA phase, a controlled residual stress field is developed in the interior of the structure. The presented experimental data show that the memory activation of the SMA composite component significantly changes the residual stress distribution in the overall structure. Designing the structural arrangement of the two phases to produce a controlled residual stress field could be used to create structures that have much improved durability and damage tolerance properties.

  20. Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

    SciTech Connect

    Han, Lili; Meng, Qingping; Wang, Deli; Zhu, Yimei; Wang, Jie; Du, Xiwen; Stach, Eric A.; Xin, Huolin L.

    2016-12-08

    An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. As a result, this work characterizes the pathways that can control the morphology in binary oxide materials.

  1. Computational study of alkynes insertion into metal-hydride bonds catalyzed by bimetallic complexes.

    PubMed

    Di Tommaso, Stefania; Tognetti, Vincent; Sicilia, Emilia; Adamo, Carlo; Russo, Nino

    2010-11-01

    Density Functional Theory investigations on the insertion mechanism of phenylacetylene into metal-hydride bonds in bimetallic (Pt,Os) catalysts have been carried out. The results obtained have been also compared with the non-reactive monometallic (Os-based) system, to elucidate the cooperative effects and to explain the observed absence of reactivity. The identified reaction path involves phenylacetylene coordination followed by the insertion into the metal-hydride bond, leading to the formation of the experimentally observed products. Both steps do not require large energies compatible with the experimental conditions. The comparison with the reaction path for the monometallic species gives some hints on the cooperative effects due to the presence of the second metal which is related to its role in the CO release for creating a coordination site for phenylacetylene and not in the insertion energetics. The calculations provide a detailed analysis of the reaction complexity and provide a rationale for the efficiency of the process.

  2. Bimetallic promotion of cooperative hydrogen transfer and heteroatom removal in coal liquefaction

    SciTech Connect

    Eisch, J.J.

    1991-10-01

    The ultimate objective of this research is to uncover new catalytic processes for the liquefaction of coal and for upgrading coal-derived fuels by removing undesirable organosulfur, organonitrogen and organooxygen constituents. Basic to both the liquefaction of coal and the purification of coal liquids is the transfer of hydrogen from such sources as dihydrogen, metal hydrides or partially reduced aromatic hydrocarbons to the extensive aromatic rings in coal itself or to aromatic sulfides, amines or ethers. Accordingly, this study is exploring how such crucial hydrogen-transfer processes might be catalyzed by soluble, low-valent transition metal complexes and/or Lewis acids under moderate conditions of temperature and pressure. By learning the mechanism whereby H{sub 2}, metal hydrides or partially hydrogenated aromatics do transfer hydrogen to model aromatic compounds, with the aid of homogeneous, bimetallic catalysts, we hope to identify new methods for producing superior fuels from coal.

  3. Formation mechanism for the nanoscale amorphous interface in pulse-welded Al/Fe bimetallic systems

    NASA Astrophysics Data System (ADS)

    Li, Jingjing; Yu, Qian; Zhang, Zijiao; Xu, Wei; Sun, Xin

    2016-05-01

    Pulse or impact welding traditionally has been referred to as "solid-state" welding. By integrating advanced interface characterizations and diffusion calculations, we report that the nanoscale amorphous interface in the pulse-welded Al/Fe bimetallic system is formed by rapid heating and melting of a thin Al layer at the interface, diffusion of iron atoms in the liquid aluminum, and subsequent rapid quenching with diffused iron atoms in solution. This finding challenges the commonly held belief regarding the solid-state nature of the impact-based welding process for dissimilar metals. Elongated ultra-fine grains with high dislocation density and ultra-fine equiaxed grains also are observed in the weld interface vicinity on the steel and aluminum sides, respectively, which further confirms that melting and the subsequent recrystallization occurred on the aluminum side of the interface.

  4. Synthesis of Co-based bimetallic nanocrystals with one-dimensional structure for selective control on syngas conversion

    NASA Astrophysics Data System (ADS)

    Ba, Rongbin; Zhao, Yonghui; Yu, Lujing; Song, Jianjun; Huang, Shuangshuang; Zhong, Liangshu; Sun, Yuhan; Zhu, Yan

    2015-07-01

    Co-based bimetallic nanocrystals with one-dimensional (1D) branches were synthesized by the heterogeneous nucleation of Co atoms onto prenucleated seeds, such as Pd or Cu, through a facile wet-chemical route. The peripheral branches (rod-like) of the Co-Pd and Co-Cu nanocrystals were outspread along the (001) direction and were enclosed by (101) facets. By switching the prenucleated metals to form robust Co-Pd or Co-Cu bimetallic nanocatalysts, the selectivity of CO hydrogenation could be adjusted purposely towards heavy paraffins, light olefins or oxygenates. The Anderson-Schulz-Flory chain-lengthening probabilities for products were up to 0.9 over Co-Pd nanocrystals, showing that long-chain hydrocarbons can be formed with high selectivity using the targeted design of Co-Pd nanocrystal catalysts. These Co-based bimetallic nanocrystals with a 1D structure exhibited superior catalytic activities over the corresponding Co-based nanoparticles for synthesis gas conversion.Co-based bimetallic nanocrystals with one-dimensional (1D) branches were synthesized by the heterogeneous nucleation of Co atoms onto prenucleated seeds, such as Pd or Cu, through a facile wet-chemical route. The peripheral branches (rod-like) of the Co-Pd and Co-Cu nanocrystals were outspread along the (001) direction and were enclosed by (101) facets. By switching the prenucleated metals to form robust Co-Pd or Co-Cu bimetallic nanocatalysts, the selectivity of CO hydrogenation could be adjusted purposely towards heavy paraffins, light olefins or oxygenates. The Anderson-Schulz-Flory chain-lengthening probabilities for products were up to 0.9 over Co-Pd nanocrystals, showing that long-chain hydrocarbons can be formed with high selectivity using the targeted design of Co-Pd nanocrystal catalysts. These Co-based bimetallic nanocrystals with a 1D structure exhibited superior catalytic activities over the corresponding Co-based nanoparticles for synthesis gas conversion. Electronic supplementary

  5. Fabrication of electrically conductive nickel-silver bimetallic particles via polydopamine coating.

    PubMed

    Kim, Sung Yeop; Kim, Jieun; Choe, Jaehoon; Byun, Young Chang; Seo, Jung Hyun; Kim, Do Hyun

    2013-11-01

    Inspired by adhesive proteins excreted by marine mussels, dopamine can act as a versatile surface modification agent for various organic and inorganic materials. By using adhesive polydopamine (PDA) as an intermediate layer, a simple and novel method for fabricating nickel-PDA-silver (Ni-PDA-Ag) bimetallic composite particles was developed. Ni-PDA-Ag bimetallic particles were fabricated by dispersing Ni particles in an aqueous dopamine solution followed by electroless Ag plating on the prepared Ni-PDA particles. A PDA layer with nano-meter thickness was deposited spontaneously on the surface of the Ni particles by oxidative self-polymerization of dopamine under alkaline conditions. Electroless Ag plating on the prepared Ni-PDA particles was carried out in the presence of a glucose solution as a reducing agent. Ni-PDA particles and Ni-PDA-Ag composite particles with a PDA intermediate layer were characterized by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), field-emission transmission electron microscopy (FE-TEM), and X-ray diffraction (XRD). In addition, the electrical conductivity of as-prepared composite particles was evaluated by a 4-point probe. The PDA layer deposited on the surface of Ni was confirmed by XPS spectra, FT-IR spectroscopy, and FE-TEM. FE-SEM images demonstrated that Ag nanoparticles were successfully plated on the PDA layer-coated Ni particles after the electroless Ag plating process. XRD patterns also confirmed the presence of Ag in a metallic state. In addition, the sheet resistance of as-prepared composite particles showed a tendency to decrease with increasing AgNO3 concentration.

  6. A highly sensitive non-enzymatic glucose sensor based on bimetallic Cu-Ag superstructures.

    PubMed

    Li, Hua; Guo, Chun-Yan; Xu, Cai-Ling

    2015-01-15

    Bimetallic Cu-Ag superstructures were successfully fabricated for the first time by using the natural leaves as reducing agent through a facile one-step hydrothermal process. Morphology, structure and composition of the Cu-Ag superstructures were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES), respectively. The results reveal that the Cu-Ag superstructure is bimetallic nanocomposite constructed by nanoparticles with low Ag content and shows a rough surface and porous flexural algae-like microstructure. By using a three-dimensional nickel foam as the scaffold, a novel non-enzymatic glucose sensor based on Cu-Ag nanocomposites has been fabricated and applied to non-enzymatic glucose detection. The as-prepared Cu-Ag nanocomposites based glucose sensor displays distinctly enhanced electrocatalytic activity compared to those obtained with pure Cu nanomaterials prepared with a similar procedure, revealing a synergistic effect of the matrix Cu and the doped Ag. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy indicate that the Cu-Ag superstructures based glucose sensor displays a fascinating sensitivity up to 7745.7 μA mM(-1) cm(-2), outstanding detection limit of 0.08 μM and fast amperometric response (<2 s) for glucose detection. Furthermore, the sensor also exhibits significant selectivity, excellent stability and reproducibility, as well as attractive feasibility for real sample analysis. Because of its excellent electrochemical performance, low cost and easy preparation, this novel electrode material is a promising candidate in the development of non-enzymatic glucose sensor.

  7. Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

    NASA Astrophysics Data System (ADS)

    Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

    2017-02-01

    In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

  8. Novel platinum–palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities

    PubMed Central

    Ghosh, Sougata; Nitnavare, Rahul; Dewle, Ankush; Tomar, Geetanjali B; Chippalkatti, Rohan; More, Piyush; Kitture, Rohini; Kale, Sangeeta; Bellare, Jayesh; Chopade, Balu A

    2015-01-01

    Medicinal plants serve as rich sources of diverse bioactive phytochemicals that might even take part in bioreduction and stabilization of phytogenic nanoparticles with immense therapeutic properties. Herein, we report for the first time the rapid efficient synthesis of novel platinum–palladium bimetallic nanoparticles (Pt–PdNPs) along with individual platinum (PtNPs) and palladium (PdNPs) nanoparticles using a medicinal plant, Dioscorea bulbifera tuber extract (DBTE). High-resolution transmission electron microscopy revealed monodispersed PtNPs of size 2–5 nm, while PdNPs and Pt–PdNPs between 10 and 25 nm. Energy dispersive spectroscopy analysis confirmed 30.88%±1.73% elemental Pt and 68.96%±1.48% elemental Pd in the bimetallic nanoparticles. Fourier transform infrared spectra indicated strong peaks at 3,373 cm−1, attributed to hydroxyl group of polyphenolic compounds in DBTE that might play a key role in bioreduction in addition to the sharp peaks at 2,937, 1,647, 1,518, and 1,024 cm−1, associated with C–H stretching, N–H bending in primary amines, N–O stretching in nitro group, and C–C stretch, respectively. Anticancer activity against HeLa cells showed that Pt–PdNPs exhibited more pronounced cell death of 74.25% compared to individual PtNPs (12.6%) or PdNPs (33.15%). Further, Pt–PdNPs showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl, superoxide, nitric oxide, and hydroxyl radicals. PMID:26719690

  9. Low-temperature aqueous-phase reforming of ethanol on bimetallic PdZn catalysts

    SciTech Connect

    Xiong, Haifeng; DelaRiva, Andrew; Wang, Yong; Dayte, Abhaya

    2015-01-01

    Bimetallic PdZn catalysts supported on carbon black (CB) and carbon nanotubes (CNTs) were found to be selective for CO-free H-2 production from ethanol at low temperature (250 degrees C). On Pd, the H-2 yield was low (similar to 0.3 mol H-2/mol ethanol reacted) and the CH4/CO2 ratio was high (similar to 1.7). Addition of Zn to Pd formed the intermetallic PdZn beta phase (atomic ratio of Zn to Pd is 1) with increased H-2 yield (similar to 1.9 mol H-2/mol ethanol reacted) and CH4/CO2 ratio of <1. The higher H-2 yield and low CH4 formation was related to the improved dehydrogenation activity of the L1(0) PdZn beta phase. The TOF increased with particle size and the CNTs provided the most active and selective catalysts, which may be ascribed to pore-confinement effects. Furthermore, no significant changes in either the supports or the PdZn beta particles was found after aqueous-phase reforming (APR) indicating that the metal nanoparticles and the carbon support are hydrothermally stable in the aqueous phase at elevated temperatures and pressures (>200 degrees C, 65 bar). No CO was detected for all the catalysts performed in aqueous-phase reaction, indicating that both monometallic Pd and bimetallic PdZn catalysts have high water-gas shift activity during APR. However, the yield of H-2 is considerably lower than the theoretical value of 6 H-2 per mole ethanol which is due to the presence of oxygenated products and methane on the PdZn catalysts.

  10. Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution

    NASA Astrophysics Data System (ADS)

    Zhong, Jin-Hui; Jin, Xi; Meng, Lingyan; Wang, Xiang; Su, Hai-Sheng; Yang, Zhi-Lin; Williams, Christopher T.; Ren, Bin

    2016-11-01

    An atomic- and molecular-level understanding of heterogeneous catalysis is required to characterize the nature of active sites and improve the rational design of catalysts. Achieving this level of characterization requires techniques that can correlate catalytic performances to specific surface structures, so as to avoid averaging effects. Tip-enhanced Raman spectroscopy combines scanning probe microscopy with plasmon-enhanced Raman scattering and provides simultaneous topographical and chemical information at the nano/atomic scale from ambient to ultrahigh-vacuum and electrochemical environments. Therefore, it has been used to monitor catalytic reactions and is proposed to correlate the local structure and function of heterogeneous catalysts. Bimetallic catalysts, such as Pd-Au, show superior performance in various catalytic reactions, but it has remained challenging to correlate structure and reactivity because of their structural complexity. Here, we show that TERS can chemically and spatially probe the site-specific chemical (electronic and catalytic) and physical (plasmonic) properties of an atomically well-defined Pd(sub-monolayer)/Au(111) bimetallic model catalyst at 3 nm resolution in real space using phenyl isocyanide as a probe molecule (Fig. 1a). We observe a weakened N≡C bond and enhanced reactivity of phenyl isocyanide adsorbed at the Pd step edge compared with that at the Pd terrace. Density functional theory corroborates these observations by revealing a higher d-band electronic profile for the low-coordinated Pd step edge atoms. The 3 nm spatial resolution we demonstrate here is the result of an enhanced electric field and distinct electronic properties at the step edges.

  11. Design, Development and Hotfire Testing of Monolithic Copper and Bimetallic Additively Manufactured Combustion Chambers

    NASA Technical Reports Server (NTRS)

    Gradl, Paul; Barnett, Greg; Brandsmeier, Will; Greene, Sandy Elam; Protz, Chris

    2016-01-01

    NASA and industry partners are working towards fabrication process development to reduce costs and schedules associated with manufacturing liquid rocket engine components with the goal of reducing overall mission costs. One such technique being evaluated is powder-bed fusion or selective laser melting (SLM) otherwise commonly referred to as additive manufacturing. The NASA Low Cost Upper Stage Propulsion (LCUSP) program was designed to develop processes and material characterization for the GRCop-84 copper-alloy commensurate with powder bed additive manufacturing, evaluate bimetallic deposition and complete testing of a full scale combustion chamber. As part of this development, the process has been transferred to industry partners to enable a long-term supply chain of monolithic copper combustion chambers. As a direct spin off of this program, NASA is working with industry partners to further develop the printing process for the GRCop-84 material in addition to the C-18150 (CuCrZr) material. To advance the process further and allow for optimization with multiple materials, NASA is also investigating the feasibility of bimetallic additively manufactured chambers. A 1.2k sized thrust-chamber was designed and developed to compare the printing process of the GRCop-84 and C-18150 SLM materials. A series of similar MCC liners also completed development with an Inconel 625 jacket bonded to the GRcop-84 liner evaluating direct metal deposition (DMD) laser and arc-based techniques. This paper describes the design, development, manufacturing and testing of these combustion chambers and associated lessons learned throughout the design and development process.

  12. Novel platinum-palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities.

    PubMed

    Ghosh, Sougata; Nitnavare, Rahul; Dewle, Ankush; Tomar, Geetanjali B; Chippalkatti, Rohan; More, Piyush; Kitture, Rohini; Kale, Sangeeta; Bellare, Jayesh; Chopade, Balu A

    2015-01-01

    Medicinal plants serve as rich sources of diverse bioactive phytochemicals that might even take part in bioreduction and stabilization of phytogenic nanoparticles with immense therapeutic properties. Herein, we report for the first time the rapid efficient synthesis of novel platinum-palladium bimetallic nanoparticles (Pt-PdNPs) along with individual platinum (PtNPs) and palladium (PdNPs) nanoparticles using a medicinal plant, Dioscorea bulbifera tuber extract (DBTE). High-resolution transmission electron microscopy revealed monodispersed PtNPs of size 2-5 nm, while PdNPs and Pt-PdNPs between 10 and 25 nm. Energy dispersive spectroscopy analysis confirmed 30.88% ± 1.73% elemental Pt and 68.96% ± 1.48% elemental Pd in the bimetallic nanoparticles. Fourier transform infrared spectra indicated strong peaks at 3,373 cm(-1), attributed to hydroxyl group of polyphenolic compounds in DBTE that might play a key role in bioreduction in addition to the sharp peaks at 2,937, 1,647, 1,518, and 1,024 cm(-1), associated with C-H stretching, N-H bending in primary amines, N-O stretching in nitro group, and C-C stretch, respectively. Anticancer activity against HeLa cells showed that Pt-PdNPs exhibited more pronounced cell death of 74.25% compared to individual PtNPs (12.6%) or PdNPs (33.15%). Further, Pt-PdNPs showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl, superoxide, nitric oxide, and hydroxyl radicals.

  13. Nanostructured catalysts for organic transformations.

    PubMed

    Chng, Leng Leng; Erathodiyil, Nandanan; Ying, Jackie Y

    2013-08-20

    The development of green, sustainable and economical chemical processes is one of the major challenges in chemistry. Besides the traditional need for efficient and selective catalytic reactions that will transform raw materials into valuable chemicals, pharmaceuticals and fuels, green chemistry also strives for waste reduction, atomic efficiency and high rates of catalyst recovery. Nanostructured materials are attractive candidates as heterogeneous catalysts for various organic transformations, especially because they meet the goals of green chemistry. Researchers have made significant advances in the synthesis of well-defined nanostructured materials in recent years. Among these are novel approaches that have permitted the rational design and synthesis of highly active and selective nanostructured catalysts by controlling the structure and composition of the active nanoparticles (NPs) and by manipulating the interaction between the catalytically active NP species and their support. The ease of isolation and separation of the heterogeneous catalysts from the desired organic product and the recovery and reuse of these NPs further enhance their attractiveness as green and sustainable catalysts. This Account reviews recent advances in the use of nanostructured materials for catalytic organic transformations. We present a broad overview of nanostructured catalysts used in different types of organic transformations including chemoselective oxidations and reductions, asymmetric hydrogenations, coupling reactions, C-H activations, oxidative aminations, domino and tandem reactions, and more. We focus on recent research efforts towards the development of the following nanostructured materials: (i) nanostructured catalysts with controlled morphologies, (ii) magnetic nanocomposites, (iii) semiconductor-metal nanocomposites, and (iv) hybrid nanostructured catalysts. Selected examples showcase principles of nanoparticle design such as the enhancement of reactivity, selectivity

  14. Carbon nanostructures for orthopedic medical applications.

    PubMed

    Yang, Lei; Zhang, Lijuan; Webster, Thomas J

    2011-09-01

    Carbon nanostructures (including carbon nanofibers, nanostructured diamond, fullerene materials and so forth) possess extraordinary physiochemical, mechanical and electrical properties attractive to bioengineers and medical researchers. In the past decade, numerous developments towards the fabrication and biological studies of carbon nanostructures have provided opportunities to improve orthopedic applications. Therefore, the aim of this article is to provide an up-to-date review on carbon nanostructure advances in orthopedic research. Orthopedic medical device applications of carbon nanotubes/carbon nanofibers and nanostructured diamond (including particulate nanodiamond and nanocrystalline diamond coatings) are emphasized here along with other carbon nanostructures that have promising potential. In addition, widely used fabrication techniques for producing carbon nanostructures in both the laboratory and in industry are briefly introduced. In conclusion, carbon nanostructures have demonstrated tremendous promise for orthopedic medical device applications to date, and although some safety, reliability and durability issues related to the manufacturing and implantation of carbon nanomaterials remain, their future is bright.

  15. Key Physical Mechanisms in Nanostructured Solar Cells

    SciTech Connect

    Dr Stephan Bremner

    2010-07-21

    The objective of the project was to study both theoretically and experimentally the excitation, recombination and transport properties required for nanostructured solar cells to deliver energy conversion efficiencies well in excess of conventional limits. These objectives were met by concentrating on three key areas, namely, investigation of physical mechanisms present in nanostructured solar cells, characterization of loss mechanisms in nanostructured solar cells and determining the properties required of nanostructured solar cells in order to achieve high efficiency and the design implications.

  16. Semiconductor nanostructure-based photovoltaic solar cells.

    PubMed

    Zhang, Genqiang; Finefrock, Scott; Liang, Daxin; Yadav, Gautam G; Yang, Haoran; Fang, Haiyu; Wu, Yue

    2011-06-01

    Substantial efforts have been devoted to design, synthesize, and integrate various semiconductor nanostructures for photovoltaic (PV) solar cells. In this article, we will review the recent progress in this exciting area and cover the material chemistry and physics related to all-inorganic nanostructure solar cells, hybrid inorganic nanostructure-conductive polymer composite solar cells, and dye-sensitized solar cells.

  17. Nanostructured materials in electroanalysis of pharmaceuticals.

    PubMed

    Rahi, A; Karimian, K; Heli, H

    2016-03-15

    Basic strategies and recent developments for the enhancement of the sensory performance of nanostructures in the electroanalysis of pharmaceuticals are reviewed. A discussion of the properties of nanostructures and their application as modified electrodes for drug assays is presented. The electrocatalytic effect of nanostructured materials and their application in determining low levels of drugs in pharmaceutical forms and biofluids are discussed.

  18. Semiconductor nanostructure-based photovoltaic solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Genqiang; Finefrock, Scott; Liang, Daxin; Yadav, Gautam G.; Yang, Haoran; Fang, Haiyu; Wu, Yue

    2011-06-01

    Substantial efforts have been devoted to design, synthesize, and integrate various semiconductor nanostructures for photovoltaic (PV) solar cells. In this article, we will review the recent progress in this exciting area and cover the material chemistry and physics related to all-inorganic nanostructure solar cells, hybrid inorganic nanostructure-conductive polymer composite solar cells, and dye-sensitized solar cells.

  19. Method of fabrication of anchored nanostructure materials

    DOEpatents

    Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

    2013-11-26

    Methods for fabricating anchored nanostructure materials are described. The methods include heating a nano-catalyst under a protective atmosphere to a temperature ranging from about 450.degree. C. to about 1500.degree. C. and contacting the heated nano-catalysts with an organic vapor to affix carbon nanostructures to the nano-catalysts and form the anchored nanostructure material.

  20. Interfacing nanostructures to biological cells

    DOEpatents

    Chen, Xing; Bertozzi, Carolyn R.; Zettl, Alexander K.

    2012-09-04

    Disclosed herein are methods and materials by which nanostructures such as carbon nanotubes, nanorods, etc. are bound to lectins and/or polysaccharides and prepared for administration to cells. Also disclosed are complexes comprising glycosylated nanostructures, which bind selectively to cells expressing glycosylated surface molecules recognized by the lectin. Exemplified is a complex comprising a carbon nanotube functionalized with a lipid-like alkane, linked to a polymer bearing repeated .alpha.-N-acetylgalactosamine sugar groups. This complex is shown to selectively adhere to the surface of living cells, without toxicity. In the exemplified embodiment, adherence is mediated by a multivalent lectin, which binds both to the cells and the .alpha.-N-acetylgalactosamine groups on the nanostructure.

  1. Nanostructure Neutron Converter Layer Development

    NASA Technical Reports Server (NTRS)

    Park, Cheol (Inventor); Sauti, Godfrey (Inventor); Kang, Jin Ho (Inventor); Lowther, Sharon E. (Inventor); Thibeault, Sheila A. (Inventor); Bryant, Robert G. (Inventor)

    2016-01-01

    Methods for making a neutron converter layer are provided. The various embodiment methods enable the formation of a single layer neutron converter material. The single layer neutron converter material formed according to the various embodiments may have a high neutron absorption cross section, tailored resistivity providing a good electric field penetration with submicron particles, and a high secondary electron emission coefficient. In an embodiment method a neutron converter layer may be formed by sequential supercritical fluid metallization of a porous nanostructure aerogel or polyimide film. In another embodiment method a neutron converter layer may be formed by simultaneous supercritical fluid metallization of a porous nanostructure aerogel or polyimide film. In a further embodiment method a neutron converter layer may be formed by in-situ metalized aerogel nanostructure development.

  2. Zinc stannate nanostructures: hydrothermal synthesis

    PubMed Central

    Baruah, Sunandan; Dutta, Joydeep

    2011-01-01

    Nanostructured binary semiconducting metal oxides have received much attention in the last decade owing to their unique properties rendering them suitable for a wide range of applications. In the quest to further improve the physical and chemical properties, an interest in ternary complex oxides has become noticeable in recent times. Zinc stannate or zinc tin oxide (ZTO) is a class of ternary oxides that are known for their stable properties under extreme conditions, higher electron mobility compared to its binary counterparts and other interesting optical properties. The material is thus ideal for applications from solar cells and sensors to photocatalysts. Among the different methods of synthesizing ZTO nanostructures, the hydrothermal method is an attractive green process that is carried out at low temperatures. In this review, we summarize the conditions leading to the growth of different ZTO nanostructures using the hydrothermal method and delve into a few of its applications reported in the literature. PMID:27877377

  3. PREFACE: Self-organized nanostructures

    NASA Astrophysics Data System (ADS)

    Rousset, Sylvie; Ortega, Enrique

    2006-04-01

    In order to fabricate ordered arrays of nanostructures, two different strategies might be considered. The `top-down' approach consists of pushing the limit of lithography techniques down to the nanometre scale. However, beyond 10 nm lithography techniques will inevitably face major intrinsic limitations. An alternative method for elaborating ultimate-size nanostructures is based on the reverse `bottom-up' approach, i.e. building up nanostructures (and eventually assemble them to form functional circuits) from individual atoms or molecules. Scanning probe microscopies, including scanning tunnelling microscopy (STM) invented in 1982, have made it possible to create (and visualize) individual structures atom by atom. However, such individual atomic manipulation is not suitable for industrial applications. Self-assembly or self-organization of nanostructures on solid surfaces is a bottom-up approach that allows one to fabricate and assemble nanostructure arrays in a one-step process. For applications, such as high density magnetic storage, self-assembly appears to be the simplest alternative to lithography for massive, parallel fabrication of nanostructure arrays with regular sizes and spacings. These are also necessary for investigating the physical properties of individual nanostructures by means of averaging techniques, i.e. all those using light or particle beams. The state-of-the-art and the current developments in the field of self-organization and physical properties of assembled nanostructures are reviewed in this issue of Journal of Physics: Condensed Matter. The papers have been selected from among the invited and oral presentations of the recent summer workshop held in Cargese (Corsica, France, 17-23 July 2005). All authors are world-renowned in the field. The workshop has been funded by the Marie Curie Actions: Marie Curie Conferences and Training Courses series named `NanosciencesTech' supported by the VI Framework Programme of the European Community, by

  4. One step electrochemical synthesis of bimetallic PdAu supported on nafion–graphene ribbon film for ethanol electrooxidation

    SciTech Connect

    Shendage, Suresh S. Singh, Abilash S.; Nagarkar, Jayashree M.

    2015-10-15

    Highlights: • Electrochemical deposition of bimetallic PdAu NPs. • Highly loaded PdAu NPs are obtained. • Nafion–graphene supported PdAu NPs shows good activity for ethanol electrooxidation. - Abstract: A nafion–graphene ribbon (Nf–GR) supported bimetallic PdAu nanoparticles (PdAu/Nf–GR) catalyst was prepared by electrochemical codeposition of Pd and Au at constant potential. The prepared catalyst was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM) and X-ray diffraction analysis (XRD). The average particle size of PdAu nanoparticles (NPs) determined from XRD was 3.5 nm. The electrocatalytic activity of the PdAu/Nf–GR catalyst was examined by cyclic voltametry. It was observed that the as prepared catalyst showed efficient activity and good stability for ethanol electrooxidation in alkaline medium.

  5. Breakdown of the Hume-Rothery Rules in Sub-Nanometer-Sized Ta-Containing Bimetallic Small Clusters

    NASA Astrophysics Data System (ADS)

    Miyajima, Ken; Fukushima, Naoya; Himeno, Hidenori; Yamada, Akira; Mafuné, Fumitaka

    2009-11-01

    The Hume-Rothery rules are empirical rules to predict the solid solubility of metals. We examined whether the rules hold for sub-nanometer-sized small particles. We prepared bimetallic cluster ions in the gas phase by a double laser ablation technique. Taking advantage of the magic compositions of the bimetallic cluster ions relating to the distinguished stabilities, the coalescence or the segregation of Ta and another element in the sub-nanometer-sized clusters was discussed. It was found that W, Nb, and Mo readily coalesce with Ta, while Ag, Al, Au, Co, Cu, Fe, Hf, Ni, Pt, Ti, and V are segregated from Ta. On the basis of these results, we concluded that the Hume-Rothery rules do not hold for sub-nanometer-sized particles.

  6. Nanostructured Substrates for Optical Sensing

    PubMed Central

    Kemling, Jonathan W.; Qavi, Abraham J.; Bailey, Ryan C.

    2011-01-01

    Sensors that change color have the advantages of versatility, ease of use, high sensitivity, and low cost. The recent development of optically based chemical sensing platforms has increasingly employed substrates manufactured with advanced processing or fabrication techniques to provide precise control over shape and morphology of the sensor micro- and nano-structure. New sensors have resulted with improved capabilities for a number of sensing applications, including the detection of biomolecules and environmental monitoring. This perspective focuses on recent optical sensor devices that utilize nanostructured substrates. PMID:22174955

  7. Vortex ice in nanostructured superconductors

    SciTech Connect

    Reichhardt, Charles; Reichhardt, Cynthia J; Libal, Andras J

    2008-01-01

    We demonstrate using numerical simulations of nanostructured superconductors that it is possible to realize vortex ice states that are analogous to square and kagome ice. The system can be brought into a state that obeys either global or local ice rules by applying an external current according to an annealing protocol. We explore the breakdown of the ice rules due to disorder in the nanostructure array and show that in square ice, topological defects appear along grain boundaries, while in kagome ice, individual defects appear. We argue that the vortex system offers significant advantages over other artificial ice systems.

  8. Progress toward Light-Harvesting Self-Electrophoretic Motors: Highly Efficient Bimetallic Nanomotors and Micropumps in Halogen Media.

    PubMed

    Wong, Flory; Sen, Ayusman

    2016-07-26

    We have developed a highly efficient, bubble-free autonomous nanomotor based on a nanobattery. Bimetallic silver-platinum nanorods are powered by self-electrophoresis and show speeds much higher than those of other electrophoretic motors at similar fuel concentrations. The fuel (I2) can be regenerated by exposure to ambient light, leading to renewed motion of the motor. This versatile system can also be made into a micropump that transports fluid and particles.

  9. The catalytic behavior of precisely synthesized Pt–Pd bimetallic catalysts for use as diesel oxidation catalysts

    SciTech Connect

    Wong, Andrew P.; Kyriakidou, Eleni A.; Toops, Todd J.; Regalbuto, John R.

    2016-04-17

    The demands of stricter diesel engine emission regulations have created challenges for current exhaust systems. With advances in low-temperature internal combustion engines and their operations, advances must also be made in vehicle exhaust catalysts. Most current diesel oxidation catalysts use heavy amounts of precious group metals (PGMs) for hydrocarbon (HC), CO, and NO oxidation. These catalysts are expensive and are most often synthesized with poor bimetallic interaction and dispersion. In this paper, the goal was to study the effect of aging on diesel emission abatement of Pt–Pd bimetallic nanoparticles precisely prepared with different morphologies: well dispersed core–shell vs. well dispersed homogeneously alloyed vs. poorly dispersed, poorly alloyed particles. Alumina and silica supports were studied. Particle morphology and dispersion were analyzed before and after hydrothermal treatments by XRD, EDX, and STEM. Reactivity as a function of aging was measured in simulated diesel engine exhaust. While carefully controlled bimetallic catalyst nanoparticle structure has a profound influence on initial or low temperature catalytic activity, the differences in behavior disappear with higher temperature aging as thermodynamic equilibrium is achieved. The metallic character of Pt-rich alumina-supported catalysts is such that behavior rather closely follows the Pt–Pd metal phase diagram. Nanoparticles disparately composed as well-dispersed core–shell (via seq-SEA), well-dispersed homogeneously alloyed (via co-SEA), and poorly dispersed, poorly alloyed (via co-DI) end up as well alloyed, large particles of almost the same size and activity. With Pd-rich systems, the oxidation of Pd also figures into the equilibrium, such that Pd-rich oxide phases appear in the high temperature forms along with alloyed metal cores. Finally, the small differences in activity after high temperature aging can be attributed to the synthesis methods, sequential SEA and co-DI which

  10. The catalytic behavior of precisely synthesized Pt–Pd bimetallic catalysts for use as diesel oxidation catalysts

    DOE PAGES

    Wong, Andrew P.; Kyriakidou, Eleni A.; Toops, Todd J.; ...

    2016-04-17

    The demands of stricter diesel engine emission regulations have created challenges for current exhaust systems. With advances in low-temperature internal combustion engines and their operations, advances must also be made in vehicle exhaust catalysts. Most current diesel oxidation catalysts use heavy amounts of precious group metals (PGMs) for hydrocarbon (HC), CO, and NO oxidation. These catalysts are expensive and are most often synthesized with poor bimetallic interaction and dispersion. In this paper, the goal was to study the effect of aging on diesel emission abatement of Pt–Pd bimetallic nanoparticles precisely prepared with different morphologies: well dispersed core–shell vs. well dispersedmore » homogeneously alloyed vs. poorly dispersed, poorly alloyed particles. Alumina and silica supports were studied. Particle morphology and dispersion were analyzed before and after hydrothermal treatments by XRD, EDX, and STEM. Reactivity as a function of aging was measured in simulated diesel engine exhaust. While carefully controlled bimetallic catalyst nanoparticle structure has a profound influence on initial or low temperature catalytic activity, the differences in behavior disappear with higher temperature aging as thermodynamic equilibrium is achieved. The metallic character of Pt-rich alumina-supported catalysts is such that behavior rather closely follows the Pt–Pd metal phase diagram. Nanoparticles disparately composed as well-dispersed core–shell (via seq-SEA), well-dispersed homogeneously alloyed (via co-SEA), and poorly dispersed, poorly alloyed (via co-DI) end up as well alloyed, large particles of almost the same size and activity. With Pd-rich systems, the oxidation of Pd also figures into the equilibrium, such that Pd-rich oxide phases appear in the high temperature forms along with alloyed metal cores. Finally, the small differences in activity after high temperature aging can be attributed to the synthesis methods, sequential SEA and co

  11. Enhanced Hydrodeoxygenation of m -Cresol over Bimetallic Pt–Mo Catalysts through an Oxophilic Metal-Induced Tautomerization Pathway

    DOE PAGES

    Robinson, Allison; Ferguson, Glen Allen; Gallagher, James R.; ...

    2016-05-26

    Supported bimetallic catalysts consisting of a noble metal (e.g., Pt) and an oxophilic metal (e.g., Mo) have received considerable attention for the hydrodeoxygenation of oxygenated aromatic compounds produced from biomass fast pyrolysis. Here, we report that PtMo can catalyze m-cresol deoxygenation via a pathway involving an initial tautomerization step. In contrast, the dominant mechanism on monometallic Pt/Al2O3 was found to be sequential Pt-catalyzed ring hydrogenation followed by dehydration on the support. Bimetallic Pt10Mo1 and Pt1Mo1 catalysts were found to produce the completely hydrogenated and deoxygenated product, methylcyclohexane (MCH), with much higher yields than monometallic Pt catalysts with comparable metal loadingsmore » and surface areas. Over an inert carbon support, MCH formation was found to be slow over monometallic Pt catalysts, while deoxygenation was significant for PtMo catalysts even in the absence of an acidic support material. Experimental studies of m-cresol deoxygenation together with density functional theory calculations indicated that Mo sites on the PtMo bimetallic surface dramatically lower the barrier for m-cresol tautomerization and subsequent deoxygenation. The accessibility of this pathway arises from the increased interaction between the oxygen of m-cresol and the Mo sites in the Pt surface. This interaction significantly alters the configuration of the precursor and transition states for tautomerization. Lastly, a suite of catalyst characterization techniques including X-ray absorption spectroscopy (XAS) and temperature-programmed reduction (TPR) indicate that Mo was present in a reduced state on the bimetallic surface under conditions relevant for reaction. Overall, these results suggest that the use of bifunctional metal catalysts can result in new reaction pathways that are unfavorable on monometallic noble metal catalysts.« less

  12. Facile synthesis of Pd-based bimetallic nanocrystals and their application as catalysts for methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Xi, Pinxian; Cao, Yang; Yang, Fengchun; Ma, Cai; Chen, Fengjuan; Yu, Sha; Wang, Shuai; Zeng, Zhengzhi; Zhang, Xin

    2013-06-01

    We employed an efficient and facile route to synthesise monodisperse Pd-based bimetallic nanocrystals (MPd: M = Cu, Co and Ni) via a controlled co-reduction of Pd(ii) chloride and M(ii) nitrate at 200-230 °C in the presence of oleylamine (OAm). These monodisperse Pd-based nanocrystals have small dimensions, unique structures and homogeneous morphology, thus exhibit efficient catalytic activities for methanol oxidation in alkaline solution, which is much better than commercial Pd/C with same amount of palladium. The catalytic activities of these nanocrystals followed the order of NiPd/C > CoPd/C > CuPd/C > commercial Pd/C, due to the different synergistic effects. Our results show that these Pd-based bimetallic nanocrystals can be promising as practical catalysts for methanol oxidation reactions and other catalytic reactions in further investigations.We employed an efficient and facile route to synthesise monodisperse Pd-based bimetallic nanocrystals (MPd: M = Cu, Co and Ni) via a controlled co-reduction of Pd(ii) chloride and M(ii) nitrate at 200-230 °C in the presence of oleylamine (OAm). These monodisperse Pd-based nanocrystals have small dimensions, unique structures and homogeneous morphology, thus exhibit efficient catalytic activities for methanol oxidation in alkaline solution, which is much better than commercial Pd/C with same amount of palladium. The catalytic activities of these nanocrystals followed the order of NiPd/C > CoPd/C > CuPd/C > commercial Pd/C, due to the different synergistic effects. Our results show that these Pd-based bimetallic nanocrystals can be promising as practical catalysts for methanol oxidation reactions and other catalytic reactions in further investigations. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00912b

  13. Direct writing of CoFe alloy nanostructures by focused electron beam induced deposition from a heteronuclear precursor.

    PubMed

    Porrati, F; Pohlit, M; Müller, J; Barth, S; Biegger, F; Gspan, C; Plank, H; Huth, M

    2015-11-27

    Recently, focused electron beam-induced deposition has been employed to prepare functional magnetic nanostructures with potential in nanomagnetic logic and sensing applications by using homonuclear precursor gases like Fe(CO)5 or Co2(CO)8. Here we show that an extension towards the fabrication of bi-metallic compounds is possible by using a single-source heteronuclear precursor gas. We have grown CoFe alloy magnetic nanostructures from the HFeCo3(CO)12 metal carbonyl precursor. The compositional analysis indicates that the samples contain about 80 at% of metal and 10 at% of carbon and oxygen. Four-probe magnetotransport measurements are carried out on nanowires of various sizes down to a width of 50 nm, for which a room temperature resistivity of 43 μΩcm is found. Micro-Hall magnetometry reveals that 50 nm × 250 nm nanobars of the material are ferromagnetic up to the highest measured temperature of 250 K. Finally, the transmission electron microscopy (TEM) microstructural investigation shows that the deposits consist of a bcc Co-Fe phase mixed with a FeCo2 O4 spinel oxide phase with nanograins of about 5 nm diameter.

  14. Direct writing of CoFe alloy nanostructures by focused electron beam induced deposition from a heteronuclear precursor

    NASA Astrophysics Data System (ADS)

    Porrati, F.; Pohlit, M.; Müller, J.; Barth, S.; Biegger, F.; Gspan, C.; Plank, H.; Huth, M.

    2015-11-01

    Recently, focused electron beam-induced deposition has been employed to prepare functional magnetic nanostructures with potential in nanomagnetic logic and sensing applications by using homonuclear precursor gases like Fe(CO)5 or Co2(CO)8. Here we show that an extension towards the fabrication of bi-metallic compounds is possible by using a single-source heteronuclear precursor gas. We have grown CoFe alloy magnetic nanostructures from the HFeCo3(CO)12 metal carbonyl precursor. The compositional analysis indicates that the samples contain about 80 at% of metal and 10 at% of carbon and oxygen. Four-probe magnetotransport measurements are carried out on nanowires of various sizes down to a width of 50 nm, for which a room temperature resistivity of 43 μΩcm is found. Micro-Hall magnetometry reveals that 50 nm × 250 nm nanobars of the material are ferromagnetic up to the highest measured temperature of 250 K. Finally, the transmission electron microscopy (TEM) microstructural investigation shows that the deposits consist of a bcc Co-Fe phase mixed with a FeCo2 O4 spinel oxide phase with nanograins of about 5 nm diameter.

  15. An interface facet driven Rayleigh instability in high-aspect-ratio bimetallic nanolayered composites

    NASA Astrophysics Data System (ADS)

    Zheng, Shijian; Carpenter, John S.; Wang, Jian; Mara, Nathan A.; Beyerlein, Irene J.

    2014-09-01

    One limitation hindering the structural and electrical applications of nanostructured metals is the loss of their nanostructure and strength under elevated temperatures. Nanostructured metals often have grain structures that contain a high density of triple junctions, where thermally induced instabilities commonly initiate. Prior work has resulted in fabrication of nanolayered two-phase composites that possess high-aspect ratio grains, a scarcity of triple junctions, and a thermally stable microstructure. In this work, transmission electron microscopy is used to investigate how these composites could eventually breakdown during heating. We reveal an unconventional thermal instability mechanism in this class of materials, which operates without the assistance of triple junctions. The mechanism can be rationalized by that thermally induced pinch off occurs as the result of bimetal interface faceting and can trigger a classic Rayleigh instability.

  16. Alumina-supported bimetallics of palladium alloyed with germanium, tin, lead, or antimony from organometallic precursors I. Preparation and characterization

    SciTech Connect

    Aduriz, H.R.; Bodnariuk, P. , Bahia Blanca ); Coq, B.; Figueras, F. )

    1989-09-01

    Bimetallic PdSn, PdSb, PdPb, and PdGe on alumina catalysts with a low metal content have been prepared using either chloride or organometallic precursors. For the catalysts obtained from chloride precursors no interaction was observed between the two metals, and the catalysts behaved like pure Pd/Al{sub 2}O{sub 3}. In contrast, the reactions of (C{sub 4}H{sub 9}){sub 4}Sn, (C{sub 4}H{sub 9}){sub 4}Pb, (C{sub 4}H{sub 9}){sub 4}Ge, or (C{sub 4}H{sub 9}){sub 3}Sb in n-heptane solution with reduced Pd/Al{sub 2}O{sub 3} catalyst yielded a supported alloy. The interaction between metallic palladium and the organic modifier is highly selective and leads to the formation of a well-tailored bimetallic catalyst. When these final solids are reduced at 573 or 773 K, the second metal locates preferentially at the outer layer of the bimetallic aggregates. After reduction at 773 K large metallic aggregates are obtained (particle size 15 nm), and the formation of {beta}-palladium hydride, which can be formed with pure palladium catalysts, is suppressed by the addition of a small amount of the second metal. The specific activity of the palladium surface atoms for isoprene hydrogenation is then lowered, and the selectivity increased.

  17. Sonophotodeposition of bimetallic photocatalysts Pd-Au/TiO2 : application to selective oxidation of methanol to methyl formate.

    PubMed

    Colmenares, Juan C; Lisowski, Paweł; Łomot, Dariusz; Chernyayeva, Olga; Lisovytskiy, Dmytro

    2015-05-22

    The aim of this work is to develop bimetallic Pd-Au/TiO2 P90 systems, which are highly active and selective for the photocatalytic oxidation of methanol to form methyl formate. Modification of commercial TiO2 P90 with Pd-Au nanoparticles was successfully achieved for the first time by means of a sonophotodeposition (SPD) method. The prepared materials were characterized by TEM, UV/Vis spectroscopy, X-ray photoelectron spectroscopy, and powder XRD. The Pd-Au bimetallic nanoparticles supported on titania exhibited remarkably enhanced catalytic activity in selective methanol oxidation to form methyl formate due to the synergism of Au and Pd particles, as well as the strong interaction between TiO2 and Pd-Au. SPD is a green methodology that can be used to prepare well-defined bimetallic surfaces on semiconductor supports with great promise for catalytic applications, in which selectivity can be tuned through adjustment of the surface composition.

  18. Mixed-phase Pd-Pt bimetallic alloy on graphene oxide with high activity for electrocatalytic applications

    NASA Astrophysics Data System (ADS)

    Khan, Majid; Yousaf, Ammar Bin; Chen, Mingming; Wei, Chengsha; Wu, Xibo; Huang, Ningdong; Qi, Zeming; Li, Liangbin

    2015-05-01

    Bimetallic PdPt alloy nanoparticles on graphene oxide (GO) have been prepared by a simple and facile chemical route, in which the reduction of metal precursors is carried out using CO as a reductant. Structural and morphological characterizations of GO/PdPt composites are performed using X-ray diffraction, X-ray photoelectron spectroscopy analysis and transmission electron microscopy. It is found that PdPt bimetallic nanoparticles are successfully synthesized and uniformly attached on the graphene sheets. The electrocatalytic and electrochemical properties of GO/PdPt composites including methanol oxidation reaction (MOR), oxygen reduction reaction (ORR) and methanol tolerant oxygen reduction reaction (MTORR) are studied in HClO4 aqueous solution. A significant improvement in the electrocatalytic activities is observed by increasing the atomic ratio of Pt in PdPt bimetallic alloys compared to the freestanding Pd nanoparticles on GO. The prepared GO/PdPt composites with an (Pd:Pt) atomic ratio of 40:60 exhibits higher methanol oxidation activity, higher specific ORR activity and better tolerance to CO poisoning. The results can be attributed to the collective effects of the PdPt nanoparticles and the enhanced electron transfer of graphene.

  19. Atomic structure and thermal stability of Pt-Fe bimetallic nanoparticles: from alloy to core/shell architectures.

    PubMed

    Huang, Rao; Wen, Yu-Hua; Shao, Gui-Fang; Sun, Shi-Gang

    2016-06-22

    Bimetallic nanoparticles comprising noble metal and non-noble metal have attracted intense interest over the past few decades due to their low cost and significantly enhanced catalytic performances. In this article, we have explored the atomic structure and thermal stability of Pt-Fe alloy and core-shell nanoparticles by molecular dynamics simulations. In Fe-core/Pt-shell nanoparticles, Fe with three different structures, i.e., body-centered cubic (bcc), face-centered cubic (fcc), and amorphous phases, has been considered. Our results show that Pt-Fe alloy is the most stable configuration among the four types of bimetallic nanoparticles. It has been discovered that the amorphous Fe cannot stably exist in the core and preferentially transforms into the fcc phase. The phase transition from bcc to hexagonal close packed (hcp) has also been observed in bcc-Fe-core/Pt-shell nanoparticles. In contrast, Fe with the fcc structure is the most preferred as the core component. These findings are helpful for understanding the structure-property relationships of Pt-Fe bimetallic nanoparticles, and are also of significance to the synthesis and application of noble metal based nanoparticle catalysts.

  20. Debromination of polybrominated diphenyl ethers by attapulgite-supported Fe/Ni bimetallic nanoparticles: Influencing factors, kinetics and mechanism.

    PubMed

    Liu, Zongtang; Gu, Chenggang; Ye, Mao; Bian, Yongrong; Cheng, Yinwen; Wang, Fang; Yang, Xinglun; Song, Yang; Jiang, Xin

    2015-11-15

    To enhance the removal efficiency of 2,2',4,4'-tetrabromodiphenylether (BDE47) in aqueous solutions, novel attapulgite-supported Fe/Ni bimetallic nanoparticles (A-Fe/Ni), which were characterized by a core-shell nanoparticle structure and with an average diameter of 20-40 nm, were synthesized for use in BDE47 degradation. The presence of attapulgite in bimetallic systems could reduce Fe/Ni nanoparticle aggregation and enhance their reactivity. BDE47 was degraded with a significant improvement in removal efficiency of at least 96% by A-Fe/Ni that played a reductive role in the reaction. The degradation kinetics of BDE47 by A-Fe/Ni complied with pseudo-first-order characteristics. To better understand the removal mechanism, detailed analyses were performed for several influential parameters. The improved dosage of A-Fe/Ni was found to be beneficial, and higher values of initial concentration, pH, and methanol/water ratio hindered the degradation rate, which, for example, decreased significantly in mixtures with a methanol proportion higher than 50%. The identification of BDE47 degradation products revealed a stepwise debromination from n-bromo-DE to (n-1)-bromo-DE as a possible pathway, wherein the para-Br was more easily eliminated than ortho-Br. Our findings provide insight into the removal mechanism and evidence for polybrominated diphenyl ether debromination by clay-Fe/Ni bimetallic nanoparticles.

  1. The use of mechanical alloying for the preparation of palladized magnesium bimetallic particles for the remediation of PCBs.

    PubMed

    Coutts, Janelle L; Devor, Robert W; Aitken, Brian; Hampton, Michael D; Quinn, Jacqueline W; Clausen, Christian A; Geiger, Cherie L

    2011-09-15

    The kinetic rate of dechlorination of a polychlorinated biphenyl (PCB-151) by mechanically alloyed Mg/Pd was studied for optimization of the bimetallic system. Bimetal production was first carried out in a small-scale environment using a SPEX 8000M high-energy ball mill with 4-μm-magnesium and palladium impregnated on graphite, with optimized parameters including milling time and Pd-loading. A 5.57-g sample of bimetal containing 0.1257% Pd and ball milled for 3 min resulted in a degradation rate of 0.00176 min(-1)g(-1) catalyst as the most reactive bimetal. The process was then scaled-up, using a Red Devil 5400 Twin-Arm Paint Shaker, fitted with custom plates to hold milling canisters. Optimization parameters tested included milling time, number of ball bearings used, Pd-loading, and total bimetal mass milled. An 85-g sample of bimetal containing 0.1059% Pd and ball-milled for 23 min with 16 ball bearings yielded the most reactive bimetal with a degradation rate of 0.00122 min(-1)g(-1) catalyst. Further testing showed adsorption did not hinder extraction efficiency and that dechlorination products were only seen when using the bimetallic system, as opposed to any of its single components. The bimetallic system was also tested for its ability to degrade a second PCB congener, PCB-45, and a PCB mixture (Arochlor 1254); both contaminants were seen to degrade successfully.

  2. One-dimensional ZnO nanostructures.

    PubMed

    Jayadevan, K P; Tseng, T Y

    2012-06-01

    The wide-gap semiconductor ZnO with nanostructures such as nanoparticle, nanorod, nanowire, nanobelt, nanotube has high potential for a variety of applications. This article reviews the fundamentals of one-dimensional ZnO nanostructures, including processing, structure, property, application and their processing-microstructure-property correlation. Various fabrication methods of the ZnO nanostructures including vapor-liquid-solid process, vapor-solid growth, solution growth, solvothermal growth, template-assisted growth and self-assembly are introduced. The characterization and properties of the ZnO nanostructures are described. The possible applications of these nanostructures are also discussed.

  3. Conductance fluctuations in nanostructures

    NASA Astrophysics Data System (ADS)

    Zhu, Ningjia

    1997-12-01

    In this Ph.D thesis the conductance fluctuations of different physical origins in semi-conductor nanostructures were studied using both diagrammatic analytical methods and large scale numerical techniques. In the "mixed" transport regime where both mesoscopic and ballistic features play a role, for the first time I have analytically calculated the non-universal conductance fluctuations. This mixed regime is reached when impurities are distributed near the walls of a quantum wire, leaving the center region ballistic. I have discovered that the existence of a ballistic region destroys the universal conductance fluctuations. The crossover behavior of the fluctuation amplitude from the usual quasi-1D situation to that of the mixed regime is clearly revealed, and the role of various length scales are identified. My analytical predictions were confirmed by a direct numerical simulation by evaluating the Landauer formula. In another direction, I have made several studies of conductance or resistance oscillations and fluctuations in systems with artificial impurities in the ballistic regime. My calculation gave explanations of all the experimental results concerning the classical focusing peaks of the resistance versus magnetic field, the weak localization peak in a Sinai billiard system, the formation of a chaotic billiard, and predicted certain transport features which were indeed found experimentally. I have further extended the calculation to study the Hall resistance in a four-terminal quantum dot in which there is an antidot array. From my numerical data I analyzed the classical paths of electron motion and its quantum oscillations. The results compare well with recent experimental studies on similar systems. Since these billiard systems could provide quantum chaotic dynamics, I have made a detailed study of the consequence of such dynamics. In particular I have investigated the resonant transmission of electrons in these chaotic systems, and found that the level

  4. Controlled placement and orientation of nanostructures

    DOEpatents

    Zettl, Alex K; Yuzvinsky, Thomas D; Fennimore, Adam M

    2014-04-08

    A method for controlled deposition and orientation of molecular sized nanoelectromechanical systems (NEMS) on substrates is disclosed. The method comprised: forming a thin layer of polymer coating on a substrate; exposing a selected portion of the thin layer of polymer to alter a selected portion of the thin layer of polymer; forming a suspension of nanostructures in a solvent, wherein the solvent suspends the nanostructures and activates the nanostructures in the solvent for deposition; and flowing a suspension of nanostructures across the layer of polymer in a flow direction; thereby: depositing a nanostructure in the suspension of nanostructures only to the selected portion of the thin layer of polymer coating on the substrate to form a deposited nanostructure oriented in the flow direction. By selectively employing portions of the method above, complex NEMS may be built of simpler NEMSs components.

  5. Magnetostatic interactions between wire-tube nanostructures

    NASA Astrophysics Data System (ADS)

    Salazar-Aravena, D.; Palma, J. L.; Escrig, J.

    2015-05-01

    We have investigated the magnetostatic interactions between wire-tube nanostructures. We have observed that the coercivity of the array decreases when the distance between the nanostructures decreases. Besides, when the external magnetic field is applied along the axis of the nanostructures, the two Barkhausen jumps observed for an isolated wire-tube nanostructure give rise to several minor jumps for a weakly interacting array, which eventually become a single jump for the most interacting case. Additionally, the angle θ at which maximum coercivity is obtained varies as a function of the center-to-center distance between the nanostructures, while those remanences obtained for arrays with different distances between the nanostructures coincide. In this way, the study of magnetostatic interactions between wire-tube nanostructures is an interesting topic of research in connection with potential applications where it is usually desirable to avoid such interactions or at least control them.

  6. Computer Code for Nanostructure Simulation

    NASA Technical Reports Server (NTRS)

    Filikhin, Igor; Vlahovic, Branislav

    2009-01-01

    Due to their small size, nanostructures can have stress and thermal gradients that are larger than any macroscopic analogue. These gradients can lead to specific regions that are susceptible to failure via processes such as plastic deformation by dislocation emission, chemical debonding, and interfacial alloying. A program has been developed that rigorously simulates and predicts optoelectronic properties of nanostructures of virtually any geometrical complexity and material composition. It can be used in simulations of energy level structure, wave functions, density of states of spatially configured phonon-coupled electrons, excitons in quantum dots, quantum rings, quantum ring complexes, and more. The code can be used to calculate stress distributions and thermal transport properties for a variety of nanostructures and interfaces, transport and scattering at nanoscale interfaces and surfaces under various stress states, and alloy compositional gradients. The code allows users to perform modeling of charge transport processes through quantum-dot (QD) arrays as functions of inter-dot distance, array order versus disorder, QD orientation, shape, size, and chemical composition for applications in photovoltaics and physical properties of QD-based biochemical sensors. The code can be used to study the hot exciton formation/relation dynamics in arrays of QDs of different shapes and sizes at different temperatures. It also can be used to understand the relation among the deposition parameters and inherent stresses, strain deformation, heat flow, and failure of nanostructures.

  7. A transparent nanostructured optical biosensor.

    PubMed

    He, Yuan; Li, Xiang; Que, Long

    2014-05-01

    Herein we report a new transparent nanostructured Fabry-Perot interferometer (FPI) device. The unique features of the nanostructured optical device can be summarized as the following: (i) optically transparent nanostructured optical device; (ii) simple and inexpensive for fabrication; (iii) easy to be fabricated and scaled up as an arrayed format. These features overcome the existing barriers for the current nanopore-based interferometric optical biosensors by measuring the transmitted optical signals rather than the reflected optical signals, thereby facilitating the optical testing significantly for the arrayed biosensors and thus paving the way for their potential for high throughput biodetection applications. The optically transparent nanostructures (i.e., anodic aluminum oxide nanopores) inside the FPI devices are fabricated from 2.2 microm thick lithographically patterned Al thin film on an indium tin oxide (ITO) glass substrate using a two-step anodization process. Utilizing the binding between Protein A and porcine immunoglobulin G (IgG) as a model, the detection of the bioreaction between biomolecules has been demonstrated successfully. Experiments found that the lowest detection concentration of proteins is in the range of picomolar level using current devices, which can be easily tuned into the range of femtomolar level by optimizing the performance of devices.

  8. A sustainable approach to empower the bio-based future ...

    EPA Pesticide Factsheets

    An economically viable and environmentally benign continuous flow intensified process has been developed to demonstrate the ability to upgrade biomass into potential biofuels, solvents, and pharmaceutical feedstocks using a bimetallic AgPd@g-C3N4 catalyst. Prepared for submission to Royal Society of Chemistry (RSC) journal, Green Chemistry.

  9. Sustainable Application of Pecan Nutshell Waste: Greener Synthesis of Pd-based Nanocatalysts for Electro-oxidation of Methanol

    EPA Science Inventory

    Palladium-based electrocatalysts are widely used in alkaline direct alcohol fuel cells. Thesynthesis and characterization of carbon-supported bimetallic nanoparticles (NP) of AuPdand AgPd is described using pecan nutshell extract (Carya illinoinensis) which serves asboth, reducin...

  10. Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

    SciTech Connect

    Lawal, Adeniyi; Manganaro, James; Goodall, Brian; Farrauto, Robert

    2015-03-24

    Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

  11. Advanced nanostructured materials for energy storage and conversion

    NASA Astrophysics Data System (ADS)

    Hutchings, Gregory S.

    Due to a global effort to reduce greenhouse gas emissions and to utilize renewable sources of energy, much effort has been directed towards creating new alternatives to fossil fuels. Identifying novel materials for energy storage and conversion can enable radical changes to the current fuel production infrastructure and energy utilization. The use of engineered nanostructured materials in these systems unlocks unique catalytic activity in practical configurations. In this work, research efforts have been focused on the development of nanostructured materials to address the need for both better energy conversion and storage, with applications toward Li-O2 battery electrocatalysts, electrocatalytic generation of H2, conversion of furfural to useful chemicals and fuels, and Li battery anode materials. Highly-active alpha-MnO2 materials were synthesized for use as bifunctional oxygen reduction (ORR) and evolution (OER) catalysts in Li-O2 batteries, and were evaluated under operating conditions with a novel in situ X-ray absorption spectroscopy configuration. Through detailed analysis of local coordination and oxidation states of Mn atoms at key points in the electrochemical cycle, a self-switching behavior affecting the bifunctional activity was identified and found to be critical. In an additional study of materials for lithium batteries, nanostructured TiO2 anode materials doped with first-row transition metals were synthesized and evaluated for improving battery discharge capacity and rate performance, with Ni and Co doping at low levels found to cause the greatest enhancement. In addition to battery technology research, I have also sought to find inexpensive and earth-abundant electrocatalysts to replace state-of-the-art Pt/C in the hydrogen evolution reaction (HER), a systematic computational study of Cu-based bimetallic electrocatalysts was performed. During the screening of dilute surface alloys of Cu mixed with other first-row transition metals, materials with

  12. Control of electronic and magnetic coupling via bridging ligand geometry in a bimetallic ytterbocene complex.

    PubMed

    Carlson, Christin N; Scott, Brian L; Martin, Richard L; Thompson, Joe D; Morris, David E; John, Kevin D

    2007-06-11

    The ligand 1-methyl-3,5-bis(2,2':6',2' '-terpyridin-4'-yl)benzene has been employed in the synthesis of a new bimetallic ytterbocene complex [(Cp*)2Yb](1-methyl-3,5-bis(2,2':6',2' '-terpyridin-4'-yl)benzene)[Yb(Cp*)2] (1) and the doubly oxidized congener [1]2+ in an attempt to determine the impact of the bridging ligand geometry on the magnetic/electronic properties as compared to the previously reported 1,4-analog [(Cp*)2Yb](1,4-di(terpyridyl)benzene)[Yb(Cp*)2] (2). Electrochemical, electronic, and magnetic data provide compelling evidence that the 1,3-geometry associated with the bridging ligand of 1 has done an effective job of inhibiting electronic communication between metal centers and magnetic coupling of spin carriers at room temperature as compared to 2. In fact, the physical data associated with 1 are quite similar to those reported for the monometallic analog (Cp*)2Yb(tpy) (3). In particular, the f-f profile of [1]2+ is nearly identical to that of [3]+ in its spectral features but with an almost exact doubling of the intensities. Further, the electronic coupling between metal centers as manifested in the potential separation between metal-based reduction waves has for the first time in these bimetallic ytterbocene complexes been found to go to zero for 1. Thus, the linkage isomerism at the phenyl coupling unit has induced a change in the ground-state electronic configuration from the singlet dianion-bridged (4f)13(pi*)2(4f)13 state found in 2 to the diradical-bridged (4f)13(piA*)1(piB*)1(4f)13 state in 1. This diradical formulation on the bridging ligand in 1 is supported by DFT calculations for the uncomplexed doubly reduced ligand that indicate the ground-state configuration is a singlet diradical state with the triplet-diradical state lying to slightly higher energy. Magnetic characterization of 1 is most consistent with the behavior previously observed for monometallic analogs such as 3, and there is no evidence of long-range magnetic ordering such

  13. Bimetallic effects for enhanced polar comonomer enchainment selectivity in catalytic ethylene polymerization.

    PubMed

    Rodriguez, Brandon A; Delferro, Massimiliano; Marks, Tobin J

    2009-04-29

    The synthesis and characterization of the bimetallic 2,7-di-[(2,6-diisopropylphenyl)imino]-1,8-naphthalenediolato group 10 metal polymerization catalysts {[Ni(CH(3))](2)[1,8-(O)(2)C(10)H(4)-2,7-[CH=N(2,6-(i)Pr(2)C(6)H(3))](PMe(3))(2)} and {[Ni(1-naphthyl)](2)[1,8-(O)(2)C(10)H(4)-2,7-[CH=N(2,6-(i)Pr(2)C(6)H(3))](PPh(3))(2)} [FI(2)-Ni(2)(PR(3))(2)] are presented, along with the synthesis and characterization of the mononuclear analogues {Ni(CH(3))[3-(t)Bu-2-(O)C(6)H(3)CH=N(2,6-(i)Pr(2)C(6)H(3))](PMe)(3)} and {Ni(1-naphthyl)[3-(t)Bu-2-(O)C(6)H(3)CH=N(2,6-(i)Pr(2)C(6)H(3))](PPh)(3)} [FI-Ni (PR(3))]. Monometallic Ni catalysts were also prepared by functionalizing one ligation center of the bimetallic ligand with a trimethylsilyl group (TMS), yielding {Ni(CH(3))[1,8-(O)(TMSO)C(10)H(4)-2,7-[CH=N(2,6-(i)Pr(2)C(6)H(3))](PMe(3))} [TMS-FI(2)-Ni(PMe(3))]. The FI(2)-Ni(2) catalysts exhibit significant increases in ethylene homopolymerization activity versus the monometallic analogues, as well as increased branching and methyl branch selectivity, even in the absence of a Ni(cod)(2) cocatalyst. Increasing ethylene concentrations significantly suppress branching and alter branch morphology. FI(2)-Ni(2)-mediated copolymerizations with ethylene + polar-functionalized norbornenes exhibit a 4-fold increase in comonomer incorporation versus FI-Ni, yielding copolymers with up to 10% norbornene copolymer incorporation. FI(2)-Ni(2)-catalyzed copolymerizations with ethylene + methylacrylate or methyl methacrylate incorporate up to 11% acrylate comonomer, while the corresponding mononuclear FI-Ni catalysts incorporate negligible amounts. Furthermore, the FI(2)-Ni(2)-mediated polymerizations exhibit appreciable polar solvent tolerance, turning over in the presence of ethyl ether, acetone, and even water. The mechanism by which the present cooperative effects take place is investigated, as is the nature of the copolymer microstructures produced.

  14. A Nanostructured Bifunctional platform for Sensing of Glucose Biomarker in Artificial Saliva: Synergy in hybrid Pt/Au surfaces.

    PubMed

    Raymundo-Pereira, Paulo A; Shimizu, Flávio M; Coelho, Dyovani; Piazzeta, Maria H O; Gobbi, Angelo L; Machado, Sergio A S; Oliveira, Osvaldo N

    2016-12-15

    We report on a bimetallic, bifunctional electrode where a platinum (Pt) surface was patterned with nanostructured gold (Au) fingers with different film thicknesses, which was functionalized with glucose oxidase (GOx) to yield a highly sensitive glucose biosensor. This was achieved by using selective adsorption of a self-assembled monolayer (SAM) onto Au fingers, which allowed GOx immobilization only onto the Au-SAM surface. This modified electrode was termed bifunctional because it allowed to simultaneously immobilize the biomolecule (GOx) on gold to catalyze glucose, and detect hydrogen peroxide on Pt sites. Optimized electrocatalytic activity was reached for the architecture Pt/Au-SAM/GOx with 50nm thickness of Au, where synergy between Pt and Au allowed for detection of hydrogen peroxide (H2O2) at a low applied potential (0V vs. Ag/AgCl). Detection was performed for H2O2 in the range between 4.7 and 102.7 nmol L(-1), with detection limit of 3.4×10(-9) mol L(-1) (3.4 nmol L(-1)) and an apparent Michaelis-Menten rate constant of 3.2×10(-6)molL(-1), which is considerably smaller than similar devices with monometallic electrodes. The methodology was validated by measuring glucose in artificial saliva, including in the presence of interferents. The synergy between Pt and Au was confirmed in electrochemical impedance spectroscopy measurements with an increased electron transfer, compared to bare Pt and Au electrodes. The approach for fabricating the reproducible bimetallic Pt/Au electrodes is entirely generic and may be explored for other types of biosensors and biodevices where advantage can be taken of the combination of the two metals.

  15. Fabrication of zein nanostructure

    NASA Astrophysics Data System (ADS)

    Luecha, Jarupat

    resins. The soft lithography technique was mainly used to fabricate micro and nanostructures on zein films. Zein material well-replicated small structures with the smallest size at sub micrometer scale that resulted in interesting photonic properties. The bonding method was also developed for assembling portable zein microfluidic devices with small shape distortion. Zein-zein and zein-glass microfluidic devices demonstrated sufficient strength to facilitate fluid flow in a complex microfluidic design with no leakage. Aside from the fabrication technique development, several potential applications of this environmentally friendly microfluidic device were investigated. The concentration gradient manipulation of Rhodamine B solution in zein-glass microfluidic devices was demonstrated. The diffusion of small molecules such as fluorescent dye into the wall of the zein microfluidic channels was observed. However, with this formulation, zein microfluidic devices were not suitable for cell culture applications. This pioneer study covered a wide spectrum of the implementation of the two nanotechnology approaches to advance zein biomaterial which provided proof of fundamental concepts as well as presenting some limitations. The findings in this study can lead to several innovative research opportunities of advanced zein biomaterials with broad applications. The information from the study of zein nanocomposite structure allows the packaging industry to develop the low cost biodegradable materials with physical property improvement. The information from the study of the zein microfluidic devices allows agro-industry to develop the nanotechnology-enabled microfluidic sensors fabricated entirely from biodegradable polymer for on-site disease or contaminant detection in the fields of food and agriculture.

  16. Center for Fundamental and Applied Research in Nanostructured and Lightweight Materials. Final Technical Summary

    SciTech Connect

    Mullins, Michael; Rogers, Tony; King, Julia; Keith, Jason; Cornilsen, Bahne; Allen, Jeffrey; Gilbert, Ryan; Holles, Joseph

    2010-09-28

    The core projects for this DOE-sponsored Center at Michigan Tech have focused on several of the materials problems identified by the NAS. These include: new electrode materials, enhanced PEM materials, lighter and more effective bipolar plates, and improvement of the carbon used as a current carrier. This project involved fundamental and applied research in the development and testing of lightweight and nanostructured materials to be used in fuel cell applications and for chemical synthesis. The advent of new classes of materials engineered at the nanometer level can produce materials that are lightweight and have unique physical and chemical properties. The grant was used to obtain and improve the equipment infrastructure to support this research and also served to fund seven research projects. These included: 1. Development of lightweight, thermally conductive bipolar plates for improved thermal management in fuel cells; 2. Exploration of pseudomorphic nanoscale overlayer bimetallic catalysts for fuel cells; 3. Development of hybrid inorganic/organic polymer nanocomposites with improved ionic and electronic properties; 4. Development of oriented polymeric materials for membrane applications; 5. Preparation of a graphitic carbon foam current collectors; 6. The development of lightweight carbon electrodes using graphitic carbon foams for battery and fuel cell applications; and 7. Movement of water in fuel cell electrodes.

  17. Risk Reduction Via Greener Synthesis of Noble Metal Nanostructures and Nanocomposites

    NASA Astrophysics Data System (ADS)

    Nadagouda, M. N.; Varma, R. S.

    Aqueous preparation of nanoparticles using vitamins B2 and C which can function both as reducing and capping agents are described. Bulk and shape-controlled synthesis of noble nanostructures via microwave (MW)-assisted spontaneous reduction of noble metal salts using α-D-glucose, sucrose, and maltose has been achieved. The MW method also accomplishes the cross-linking reaction of poly (vinyl alcohol) (PVA) with metallic systems such as Pt, Cu, and In; bimetallic systems, namely Pt-In, Ag-Pt, Pt-Fe, Cu-Pd, Pt-Pd and Pd-Fe; and single-walled nanotubes (SWNT), multi-walled nanotubes (MWNT), and Buckmin-sterfullerene (C-60). The strategy is extended to the formation of biodegradable carboxymethyl cellulose (CMC) composite films with noble nanometals; such metal decoration and alignment of carbon nanotubes in CMC is possible using a MW approach. The MW approach also enables the shape-controlled bulk synthesis of Ag and Fe nanorods in poly (ethylene glycol) (PEG).

  18. Synergetic effect of palladium-ruthenium nanostructures for ethanol electrooxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Monyoncho, Evans A.; Ntais, Spyridon; Soares, Felipo; Woo, Tom K.; Baranova, Elena A.

    2015-08-01

    Palladium-ruthenium nanoparticles supported on carbon PdxRu1-x/C (x = 1, 0.99, 0.95, 0.90, 0.80, 0.50) were prepared using a polyol method for ethanol electrooxidation in alkaline media. The resulting bimetallic catalysts were found to be primarily a mix of Pd metal, Ru oxides and Pd oxides. Their electrocatalytic activity towards ethanol oxidation reaction (EOR) in 1M KOH was studied using cyclic voltammetry and chronoamperometry techniques. Addition of 1-10 at.% Ru to Pd not only lowers the onset oxidation potential for EOR but also produces higher current densities at lower potentials compared to Pd by itself. Thus, Pd90Ru10/C and Pd99Ru1/C provide the current densities of up to six times those of Pd/C at -0.96 V and -0.67 V vs MSE, respectively. The current density at different potentials was found to be dependent on the surface composition of PdxRu1-x/C nanostructures. Pd90Ru10/C catalyst with more surface oxides was found to be active at lower potential compared to Pd99Ru1/C with less surface oxides, which is active at higher potentials. The steady-state current densities of the two best catalysts, Pd90Ru10/C and Pd99Ru1/C, showed minimal surface deactivation from EOR intermediates/products during chronoamperometry.

  19. General Method for Determination of the Surface Composition in Bimetallic Nanoparticle Catalysts from the L Edge X-ray Absorption Near-Edge Spectra

    SciTech Connect

    Wu, Tiapin; Childers, David; Gomez, Carolina; Karim, Ayman M.; Schweitzer, Neil; Kropf, Arthur; Wang, Hui; Bolin, Trudy B.; Hu, Yongfeng; Kovarik, Libor; Meyer, Randall; Miller, Jeffrey T.

    2012-10-08

    Bimetallic PtPd on silica nano-particle catalysts have been synthesized and their average structure determined by Pt L3 and Pd K-edge extended X-ray absorption finestructure (EXAFS) spectroscopy. The bimetallic structure is confirmed from elemental line scans by STEM for the individual 1-2 nm sized particles. A general method is described to determine the surface composition in bimetallic nanoparticles even when both metals adsorb, for example, CO. By measuring the change in the L3 X-ray absorption near-edge structure (XANES) spectra with and without CO in bimetallic particles and comparing these changes to those in monometallic particles of known size the fraction of surface atoms can be determined. The turnover rates (TOR) and neopentane hydrogenolysis and isomerization selectivities based on the surface composition suggest that the catalytic and spectroscopic properties are different from those in monometallic nano-particle catalysts. At the same neo-pentane conversion, the isomerization selectivity is higher for the PtPd catalyst while the TOR is lower than that of both Pt and Pd. As with the catalytic performance, the infrared spectra of adsorbed CO are not a linear combination of the spectra on monometallic catalysts. Density functional theory calculations indicate that the Pt-CO adsorption enthalpy increases while the Pd-CO bond energy decreases. The ability to determine the surface composition allows for a better understanding of the spectroscopic and catalytic properties of bimetallic nanoparticle catalysts.

  20. Demonstration of intramolecular energy transfer in asymmetric bimetallic ruthenium(ii) complexes.

    PubMed

    Bar, Manoranjan; Maity, Dinesh; Das, Shyamal; Baitalik, Sujoy

    2016-11-01

    A new family of bimetallic Ru(ii) complexes derived from an asymmetric bridging ligand (tpy-Hbzim-dipy) consisting of both bipyridine and terpyridine chelating sites covalently connected via phenyl-imidazole spacer were designed in this work to demonstrate intramolecular energy transfer from one component to the other in asymmetric dyads. To fine tune the photo-redox properties, both bidentate and tridentate terminal ligands in the complexes were varied systematically. Both steady state and time-resolved luminescence spectral results indicated photo-induced intramolecular energy transfer from the excited MLCT state of the [(bpy/phen)2Ru(II)(dipy-Hbzim-tpy)] component to the MLCT state of the tpy-containing unit [(dipy-Hbzim-tpy)Ru(II)(tpy-PhCH3/H2pbbzim)] in dyads with rate constant values on the order of 10(6)-10(7) s(-1). Temperature-dependent luminescence studies indicated an enhancement in the luminescence intensity and excited state lifetimes upon decreasing the temperature.

  1. Enhanced chromium (VI) removal using activated carbon modified by zero valent iron and silver bimetallic nanoparticles.

    PubMed

    Kakavandi, Babak; Kalantary, Roshanak Rezaei; Farzadkia, Mahdi; Mahvi, Amir Hossein; Esrafili, Ali; Azari, Ali; Yari, Ahmad Reza; Javid, Allah Bakhsh

    2014-01-01

    Recently, adsorption process has been introduced as a favorable and effective technique for the removal of metal ions from aqueous solutions. In the present study, bimetallic nanoparticles consisting of zero valent iron and silver were loaded on the activated carbon powder for the preparation of a new adsorbent (PAC-Fe(o)/Ag). The above adsorbent was characterized by using XRD, SEM and TEM techniqes. Experimental data were exploited for kinetic, equilibrium and thermodynamic evaluations related to the adsorption processes. The Cr(VI) adsorption process was found to be favorable at pH 3 and it reached equilibrium state within 60 min. The stirring rate did not have a significant effect on the adsorption efficiency. Furthermore, the monolayer adsorption capacity of Cr(VI) based on the Langmuir model was measured to be 100 mg/g. The experimental equilibrium data were fitted to the Freundlich adsorption and pseudo second-order models. According to the thermodynamic study, the adsorption process was spontaneous and endothermic in nature, indicating the adsorption capacity increases with increasing the temperature. The results also revealed that the synthesized composite can be potentially applied as a magnetic adsorbent to remove Cr(VI) contaminants from aqueous solutions.

  2. Influence of shell thickness on thermal stability of bimetallic Al-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Wen, John Z.; Nguyen, Ngoc Ha; Rawlins, John; Petre, Catalin F.; Ringuette, Sophie

    2014-07-01

    Aluminum-based bimetallic core-shell nanoparticles have shown promising applications in civil and defense industries. This study addresses the thermal stability of aluminum-palladium (Al-Pd) core/shell nanoparticles with a varying shell thickness of 5, 6, and 7 Å, respectively. The classic molecular dynamics (MD) simulations are performed in order to investigate the effects of the shell thickness on the ignition mechanism and subsequent energetic processes of these nanoparticles. The histograms of temperature change and structural evolution clearly show the inhibition role of the Pd shell during ignition. While the nanoparticle with a thicker shell is more thermally stable and hence requires more excess energy, stored as the potential energy of the nanoparticle and provided through numerically heating, to initiate the thermite reaction, a higher adiabatic temperature can be produced from this nanoparticle, thanks to its greater content of Pd. The two-stage thermite reactions are discussed with their activation energy based on the energy balance processes during MD heating and production. Analyses of the simulation results reveal that the inner pressure of the core-shell nanoparticle increases with both temperature and the absorbed thermal energy during heating, which may result in a breakup of the Pd shell.

  3. Hexavalent chromium removal from near natural water by copper-iron bimetallic particles.

    PubMed

    Hu, Ching-Yao; Lo, Shang-Lien; Liou, Ya-Hsuan; Hsu, Ya-Wen; Shih, Kaimin; Lin, Chin-Jung

    2010-05-01

    The reduction of hexavalent chromium (Cr(VI)) by zero-valent iron (ZVI) is self-inhibiting in near natural groundwater because insulating Fe(III)-Cr(III) (oxy)hydroxide film forms on the ZVI surface during the reaction. This study tries to overcome this deficiency by coating the surface of ZVI with copper to form copper-iron bimetallic particles. The Cr(VI) removal rate by ZVI rose significantly after the copper coating was applied. The copper loading needed for enhancing Cr(VI) removal was much higher than that needed for enhancing removal of chlorinated organic compounds or other oxidative contaminants, because of the higher oxidation potential of Cr(VI). The results of X-ray photoelectron spectroscopy (XPS) indicate that coating copper onto the surface of ZVI can not only increase the deepness of the oxidation film but also increase the oxidation state of iron in the film. This phenomenon means higher Cr(VI) removal capacity per unit weight of ZVI.

  4. Microwave Synthesis of Chitosan Capped Silver-Dysprosium Bimetallic Nanoparticles: A Potential Nanotheranosis Device.

    PubMed

    Mishra, Sandeep K; Kannan, S

    2016-12-27

    Accurate imaging of the structural and functional state of biological targets is a critical task. To amend paucities associated with individual imaging, there is high interest to develop a multifunctional theranostic devices for cancer diagnosis and therapy. Herein, chitosan coated silver/dysprosium bimetallic nanoparticles (BNPs) were synthesized through a green chemistry route and characterization results inferred that the BNPs are crystalline, spherical, and of size ∼10 nm. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectroscopy (XPS) confirm the reduced metallic states of Ag and Dy in nanoparticles. These BNPs demonstrate high emission in a second near-infrared (NIR-II, 1000-1400 nm) biological window on excitation at 808 nm. Moreover, magnetization and magnetic resonance imaging (MRI) studies perceive the inherent paramagnetic features of Dy component that displays dark T2 contrast and high relaxivity. Due to high X-ray attenuation effect, BNPs exhibit better Hounsfield unit (HU) value than the reported contrast agents. BNPs unveil good biocompatibility and also express sturdy therapeutic effect in HeLa cells when tethered with doxorubicin.

  5. Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

    PubMed

    Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

    2017-05-01

    Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH)2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells.

  6. Degradation of tetrachloromethane and tetrachloroethene by Ni/Fe bimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, Y. Y.; Liu, F.; Li, H. D.

    2009-09-01

    The study investigated the potential of nanoscale Ni/Fe bimetallic particles reduction for carbon tetrachloride (CT) and tetrachloroethene (PCE). BET specific surface areas of the laboratory synthesized Ni/Fe (2% wt.) particle, with diameter on the order of 20-60nm, was approximately 52.61m2/g. Batch studies demonstrated that rapid transformations of PCE and CT were achieved with nanoscale Ni/Fe particles. The degradation process appeared to be pseudo-first-order. Values of the surface area normalized rate coefficients (KSA) of PCE and CT for the reaction with nano Ni/Fe were 2.068mL/(m2·h), 10.08mL/(m2·h), respectively. This indicated that the degradation rate of CT was about 5 times larger than that of PCE under comparable environmental condition. Significant amounts of DCM were detected for the reaction with CT unlike the PCE transformation where ethane was the only end-product, amount to 103% of the initial PCE carbon. Both DCM (~15%) and methane (~27%) were the major end products for CT reaction. Based on the rapid rate of degradation and no or less chlorinated byproducts, the nanoscale particles technology offered great opportunities for both fundamental research and technological application for remediation of contaminated ground water.

  7. Bimetallic strip for low temperature use. [4-300/sup 0/K

    DOEpatents

    Bussiee, J.F.; Welch, D.O.; Suenaga, M.

    A class of mechanically pre-stressed structures is provided suitably bi-layer strips, consisting of a layer of group 5 transition metals in intimate contact with a layer of an intermetallic compound of transition metals with certain group 3A, 4A or 5A metals or metalloids such as Ga, In, Si, Ge, Sn, As or Sb. The changes of Young's modulus of these bi-layered combinations at temperatures in the region of somewhat above absolute zero provides a useful means of sensing temperature changes. Such bi-metallic strips may be used as control strips in thermostats, or in direct dial reading instruments. The structures are made by preparing a sandwich of a group 5B transition metal strip between the substantially thicker strips of an alloy between copper and a predetermined group 3A, 4A or 5A metal or metalloid, holding the three layers are heated, cooled the copper alloys and is removed. Removing one of the two formed interlayer alloys between the transition metal and the metal previously alloyed with copper remain.

  8. Control of Surface Segregation in Bimetallic NiCr Nanoalloys Immersed in Ag Matrix

    PubMed Central

    Bohra, Murtaza; Singh, Vidyadhar; Grammatikopoulos, Panagiotis; Toulkeridou, Evropi; Diaz, Rosa E.; Bobo, Jean-François; Sowwan, Mukhles

    2016-01-01

    Cr-surface segregation is a main roadblock encumbering many magneto-biomedical applications of bimetallic M-Cr nanoalloys (where M = Fe, Co and Ni). To overcome this problem, we developed Ni95Cr5:Ag nanocomposite as a model system, consisting of non-interacting Ni95Cr5 nanoalloys (5 ± 1 nm) immersed in non-magnetic Ag matrix by controlled simultaneous co-sputtering of Ni95Cr5 and Ag. We employed Curie temperature (TC) as an indicator of phase purity check of these nanocomposites, which is estimated to be around the bulk Ni95Cr5 value of 320 K. This confirms prevention of Cr-segregation and also entails effective control of surface oxidation. Compared to Cr-segregated Ni95Cr5 nanoalloy films and nanoclusters, we did not observe any unwanted magnetic effects such as presence Cr-antiferromagnetic transition, large non-saturation, exchange bias behavior (if any) or uncompensated higher TC values. These nanocomposites films also lose their unique magnetic properties only at elevated temperatures beyond application requirements (≥800 K), either by showing Ni-type behavior or by a complete conversion into Ni/Cr-oxides in vacuum and air environment, respectively. PMID:26750659

  9. Design and Processing of Bimetallic Aluminum Alloys by Sequential Casting Technique

    NASA Astrophysics Data System (ADS)

    Karun, Akhil S.; Hari, S.; Ebhota, Williams S.; Rajan, T. P. D.; Pillai, U. T. S.; Pai, B. C.

    2017-01-01

    Sequential casting is a facile and fairly new technique to produce functionally graded materials (FGMs) and components by controlled mold filling process. In the present investigation, functionally graded bimetallic aluminum alloys are produced by sequential gravity casting using A390-A319 and A390-A6061 alloy combinations. The control in pouring time between two melts has shown a significant effect on the quality and nature of interface bonding. The microstructure reveals good interface miscibility achieved through diffusion bonding between the alloys. A higher hardness of 160 BHN in the A390 region is obtained in both sequential cast systems, and a minimum value of 105 and 91 BHN is observed in the A319 and A6061 regions, respectively. The tensile and compression strength for A390-A319 are 337 and 490 MPa, whereas for A390-A6061, they are 364 and 401 MPa, respectively, which are significantly higher compared with the standard values of the base alloys, which confirms strong interface bonding. The A390 region shows higher wear resistance compared with other regions of the sequential cast system. The process described in this study is a potential and efficient approach to create good bonding between two different aluminum alloys to develop advanced functional and structural materials.

  10. Wnt ligands from the embryonic surface ectoderm regulate 'bimetallic strip' optic cup morphogenesis in mouse.

    PubMed

    Carpenter, April C; Smith, April N; Wagner, Heidi; Cohen-Tayar, Yamit; Rao, Sujata; Wallace, Valerie; Ashery-Padan, Ruth; Lang, Richard A

    2015-03-01

    The Wnt/β-catenin response pathway is central to many developmental processes. Here, we assessed the role of Wnt signaling in early eye development using the mouse as a model system. We showed that the surface ectoderm region that includes the lens placode expressed 12 out of 19 possible Wnt ligands. When these activities were suppressed by conditional deletion of wntless (Le-cre; Wls(fl/fl)) there were dramatic consequences that included a saucer-shaped optic cup, ventral coloboma, and a deficiency of periocular mesenchyme. This phenotype shared features with that produced when the Wnt/β-catenin pathway co-receptor Lrp6 is mutated or when retinoic acid (RA) signaling in the eye is compromised. Consistent with this, microarray and cell fate marker analysis identified a series of expression changes in genes known to be regulated by RA or by the Wnt/β-catenin pathway. Using pathway reporters, we showed that Wnt ligands from the surface ectoderm directly or indirectly elicit a Wnt/β-catenin response in retinal pigment epithelium (RPE) progenitors near the optic cup rim. In Le-cre; Wls(fl/fl) mice, the numbers of RPE cells are reduced and this can explain, using the principle of the bimetallic strip, the curvature of the optic cup. These data thus establish a novel hypothesis to explain how differential cell numbers in a bilayered epithelium can lead to shape change.

  11. Synthesis of graphene-supported monodisperse AuPd bimetallic nanoparticles for electrochemical oxidation of methanol

    NASA Astrophysics Data System (ADS)

    Xiao, Hong-Jun; Shen, Cheng-Min; Shi, Xue-Zhao; Yang, Su-Dong; Tian, Yuan; Lin, Shao-Xiong; Gao, Hong-Jun

    2015-07-01

    Monodisperse AuPd bimetallic nanoparticles (NPs) with different compositions are synthesized by using oleylamine (OAm) as reducing reagent, stabilizer, and solvent. To obtain AuPd solid solution NPs, Pd-OAm and Au-OAm precursors are firstly prepared by mixing OAm with Palladium (II) acetylacetonate (Pd(acac)2) and HAuCl4, respectively. Then Pd-OAm and Au-OAm precursor solutions are injected into a hot oleylamine solution to form AuPd NPs. The size of these NPs ranges from 6.0 to 8.0 nm and the composition is controlled by varying the precursor ratio. The AuPd NPs are loaded onto reduced graphene oxide (RGO) sheets to make catalysts. Alloy NPs show high electrocatalytic activity and stability toward methanol oxidation in the alkaline media. Their catalytic activity for methanol oxidation is found to be dependent on the NP composition. As the Pd component increases, the peak current densities during the forward scan gradually increase and reach the maximum at AuPd2. The enhancement of alloy NPs for methanol oxidation can be attributed to a synergistic effect of Au and Pd on the surface of alloy NPs. Project supported by the National Natural Science Foundation of China (Grant No. 61335006) and the National Basic Research Program of China (Grant No. 2013CBA01603).

  12. Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

    DOE PAGES

    Han, Lili; Meng, Qingping; Wang, Deli; ...

    2016-12-08

    An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-inducedmore » chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. As a result, this work characterizes the pathways that can control the morphology in binary oxide materials.« less

  13. Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

    DOE PAGES

    Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

    2015-03-16

    One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less

  14. Electrochemical way of molybdenum extraction from the Bimetallic systems of Mo-W

    NASA Astrophysics Data System (ADS)

    Kudreeva, L. K.; Nauryzbaev, M. K.; Kurbatov, A. P.; Kamysbaev, D. H.; Adilbekova, A. O.; Mukataeva, Z. S.

    2015-12-01

    Electrochemical dissolution of molybdenum and tungsten was investigated in water- dimethylsulfoxide (DMSO) media at different concentrations of lithium chloride and magnesium perchlorate. The terms of efficient extraction of molybdenum from bimetallic systems of Mo-W have been determined. The polarization curves of the electrooxidation of molybdenum in the solution of 0.25 M LiCl in the DMSO at the different rates of rotations and the scan rate equal to 50 mV/s were obtained. In the presence of the addition of water at the potential of 0.1-0.75 V the small area of polarizability occurs, then with increasing potentials above 1.5 V there is a sharp increase of the oxidation current. Comparison of the current values of anodic dissolution of molybdenum and tungsten showed that the rate of anodic dissolution of molybdenum significantly exceeds the rate of anodic dissolution of tungsten. In the case of molybdenum, the dissolution process is limited by diffusion, in the case of tungsten - by the passive film formation on the electrode surface.

  15. Mechanistic investigation of the reaction of epoxides with heterocumulenes catalysed by a bimetallic aluminium salen complex.

    PubMed

    Beattie, Christopher; North, Michael

    2014-06-23

    The bimetallic aluminium(salen) complex [(Al(salen))2O] is known to catalyse the reaction between epoxides and heterocumulenes (carbon dioxide, carbon disulfide and isocyanates) leading to five-membered ring heterocycles. Despite their apparent similarities, these three reactions have very different mechanistic features, and a kinetic study of oxazolidinone synthesis combined with previous kinetic work on cyclic carbonate and cyclic dithiocarbonate synthesis showed that all three reactions follow different rate equations. An NMR study of [Al(salen)]2O and phenylisocyanate provided evidence for an interaction between them, consistent with the rate equation data. A variable-temperature kinetics study on all three reactions showed that cyclic carbonate synthesis had a lower enthalpy of activation and a more negative entropy of activation than the other two heterocycle syntheses. The kinetic study was extended to oxazolidinone synthesis catalysed by the monometallic complex Al(salen)Cl, and this reaction was found to have a much less negative entropy of activation than any reaction catalysed by [Al(salen)]2O, a result that can be explained by the partial dissociation of an oligomeric Al(salen)Cl complex. A mechanistic rationale for all of the results is presented in terms of [Al(salen)]2O being able to function as a Lewis acid and/or a Lewis base, depending upon the susceptibility of the heterocumulene to reaction with nucleophiles.

  16. Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

    SciTech Connect

    Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; Zhou, Yang; Forest, Robert V.; Tao, Runzhe; Rosen, Jonathan; Yonemoto, Bryan T.; Cao, Zeyuan; Zheng, Haimei; Xiao, John Q.; Jiao, Feng; Chen, Jingguang G.

    2015-03-16

    One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchical porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.

  17. Synthesis and characterization of monometallic niobium carbides and bimetallic niobium carbides using hafnium, titanium, and tantalum

    NASA Astrophysics Data System (ADS)

    Watts, Cassandra Jean

    As fossil fuels are rapidly depleting there is an enormous push for the development of new forms of energy based on renewable resources. Proton Exchange Membrane (PEM) fuel cells are one possible solution, but are constrained by the necessity of the platinum catalyst to initiate the oxygen reduction reaction (ORR). Transition metal carbides, like tungsten and molybdenum carbide, have shown catalytic properties that resemble platinum. This project seeks to synthesize through a low temperature solid state method with a LiCl:KCl:KF salt flux monometallic niobium carbides (NbC, Nb4C3, and Nb2C) and the bimetallic niobium carbides HfNbC, TiNbC, and TaNbC. The synthesized materials are characterized using XRD, SEM, and EDS. The results showed that a pure single phase of NbC and Nb4C 3, and a semi alloyed phase of TiNbC2 are obtainable. The remaining systems yielded phase separated carbide systems and are dominated by irreproducibility or oxidization.

  18. Adsorption of carbon oxide on tetrahedral bimetallic gold-copper clusters

    NASA Astrophysics Data System (ADS)

    Gogol', V. V.; Pichugina, D. A.; Kuz'menko, N. E.

    2016-12-01

    The interaction between carbon oxide and [Au20-nCun]q clusters ( n = 0, 1, 19, 20 and q = 0, ±1) is studied by means of DFT/PBE in the scalar relativistic approximation. To establish the composition and structure of an adsorption site, isomers of bimetallic Au19Cu and AuCu19 particles with different positions of the heteroatom at an apex, edge, and face of the tetrahedral framework are considered. The optimized structures are used as the basis to determine the electronic properties of clusters (average bond energy per atom, difference of energies between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), ionization potential, electron affinity energy). The calculated parameters shrink as the copper content in clusters grows. Among the uncharged models, the highest CO adsorption energy is typical of Au19Cu, the heteroatom of which lies at a cluster's apex. The CO adsorption energy for cationic and anionic clusters grows in comparison to neutral clusters.

  19. Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

    NASA Astrophysics Data System (ADS)

    Félix-Navarro, R. M.; Beltrán-Gastélum, M.; Salazar-Gastélum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Pérez-Sicairos, S.; Lin, S. W.; Paraguay-Delgado, F.; Alonso-Núñez, G.

    2013-08-01

    Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O2 to H2O2. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H2SO4 electrolyte using dissolved O2. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H2O2 electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H2O2 alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

  20. Reforming and oxidative dehydrogenation of ethane with CO2 as a soft oxidant over bimetallic catalysts

    DOE PAGES

    Myint, MyatNoeZin; Yan, Binhang; Wan, Jie; ...

    2016-02-26

    An efficient mitigation of abundantly available CO2 is critical for sustainable environmental impact as well as for novel industrial applications. Using ethane, CO2 can be catalytically converted into a useful feedstock (synthesis gas) and a value-added monomer (ethylene) via the dry reforming pathway through the C–C bond scission and the oxidative dehydrogenation pathway through the C–H bond scission, respectively. Results from the current flow-reactor study show that the precious metal bimetallic CoPt/CeO2 catalyst undergoes the reforming reaction to produce syngas with enhanced activity and stability compared to the parent monometallic catalysts. In this paper, in order to replace Pt, themore » activities of non-precious CoMo/CeO2 and NiMo/CeO2 are investigated and the results indicate that NiMo/CeO2 is nearly as active as CoPt/CeO2 for the reforming pathway. Furthermore, FeNi/CeO2 is identified as a promising catalyst for the oxidative dehydrogenation to produce ethylene. Finally, density functional theory (DFT) calculations are performed to further understand the different pathways of the CoPt/CeO2 and FeNi/CeO2 catalysts.« less

  1. Dual-frequency plasmon lasing modes in active three-layered bimetallic Ag/Au nanoshells

    NASA Astrophysics Data System (ADS)

    Wu, DaJian; Wu, XueWei; Cheng, Ying; Jin, BiaoBing; Liu, XiaoJun

    2015-11-01

    The optical properties of three-layered silver-gold-silica (SGS) nanoshells with gain have been investigated theoretically by using Mie theory. Surface plasmon amplification by stimulated emission of radiation (spaser) phenomena can be observed at two plasmon modes of the active SGS nanoshell in the visible region. It is found with the decrease in the radius of the inner Ag core that the critical value of ɛg″(ωg ) for the super-resonance of the low-energy mode increases first and then decreases while that for the high-energy mode decreases. An interesting overlap between the two curves for the critical value of ɛg″(ωg ) can be found at a special core radius. At this point, two super-resonances can be achieved concurrently at the low- and high-energy modes of the active SGS nanoshell with the same gain coefficient. This dual-frequency spaser based on the bimetallic Ag/Au nanoshell may be an efficient candidate for designing the nanolaser.

  2. Combination of supported bimetallic rhodium–molybdenum catalyst and cerium oxide for hydrogenation of amide

    PubMed Central

    Nakagawa, Yoshinao; Tamura, Riku; Tamura, Masazumi; Tomishige, Keiichi

    2015-01-01

    Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6–7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh–MoOx/SiO2, and the addition of CeO2 much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2–8 MPa and 393–433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh–MoOx/SiO2 + CeO2 was 63%. The effect of CeO2 addition was highest when CeO2 was not calcined, and CeO2 calcined at >773 K showed a smaller effect. The use of CeO2 as a support rather decreased the activity in comparison with Rh–MoOx/SiO2. The weakly-basic nature of CeO2 additive can affect the surface structure of Rh–MoOx/SiO2, i.e. reducing the ratio of Mo–OH/Mo–O− sites. PMID:27877749

  3. Combination of supported bimetallic rhodium-molybdenum catalyst and cerium oxide for hydrogenation of amide

    NASA Astrophysics Data System (ADS)

    Nakagawa, Yoshinao; Tamura, Riku; Tamura, Masazumi; Tomishige, Keiichi

    2015-02-01

    Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6-7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh-MoOx/SiO2, and the addition of CeO2 much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2-8 MPa and 393-433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh-MoOx/SiO2 + CeO2 was 63%. The effect of CeO2 addition was highest when CeO2 was not calcined, and CeO2 calcined at >773 K showed a smaller effect. The use of CeO2 as a support rather decreased the activity in comparison with Rh-MoOx/SiO2. The weakly-basic nature of CeO2 additive can affect the surface structure of Rh-MoOx/SiO2, i.e. reducing the ratio of Mo-OH/Mo-O- sites.

  4. Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

    PubMed Central

    Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; Zhou, Yang; Forest, Robert V.; Tao, Runzhe; Rosen, Jonathan; Yonemoto, Bryan T.; Cao, Zeyuan; Zheng, Haimei; Xiao, John Q.; Jiao, Feng; Chen, Jingguang G.

    2015-01-01

    A robust and efficient non-precious metal catalyst for hydrogen evolution reaction is one of the key components for carbon dioxide-free hydrogen production. Here we report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the-art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. In addition, the hierarchical porosity of the nanoporous copper-titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface. PMID:25910892

  5. Glucose microfluidic fuel cell based on silver bimetallic selective catalysts for on-chip applications

    NASA Astrophysics Data System (ADS)

    Cuevas-Muñiz, F. M.; Guerra-Balcázar, M.; Esquivel, J. P.; Sabaté, N.; Arriaga, L. G.; Ledesma-García, J.

    2012-10-01

    A glucose microfluidic fuel cell with outstanding performance at zero flow condition is presented. Polarization tests showed that bimetallic materials based in silver (AuAg/C as anode, PtAg/C as cathode) exhibit tolerance to byproducts and crossover effect. This allowed achieving one of the highest power densities reported for glucose fuel cells, up to a value of 630 μW cm-2 using two separated laminar flows of reactants. Furthermore, the tolerance to crossover effect caused by the selectivity of PtAg/C to oxygen reduction reaction in presence of glucose permitted using a single flow containing a mixture of glucose/oxygen, yielding a performance as high as 270 μW cm-2. Microfluidic fuel cell was further evaluated with a simulated body fluid solution that contained salts commonly present in the human blood plasma, reaching a power of 240 μW cm-2 at zero flow. These results envisage the incorporation of this fuel cell as a portable power source in Lab-on-a-Chip devices without the need of external pumps.

  6. Growth and characterization of bimetallic (Na and K) phthalate single crystals

    NASA Astrophysics Data System (ADS)

    Amuthambigai, C.; Mahadevan, C. K.; Sahaya Shajan, X.

    2016-10-01

    Bimetallic (Na and K) phthalate single crystals were grown by the solvent evaporation method and characterized. X-ray diffraction (single crystal and powder), Fourier transform infrared spectral and atomic absorption spectral measurements indicate a centrosymmetric trigonal crystal system (space group Pbar{3}1c) with chemical composition as Na0.51K1.49C8O4H4.H2O. UV-Vis-NIR spectral measurement indicates an optical transmittance of 72 % in the wavelength range 300-1200 nm. The crystal is found to be nonlinear optically active due to local non-centrosymmetry. Thermal and mechanical stabilities of the grown crystal were examined by thermogravimetric and microhardness measurements. Electrical (both AC, with various frequencies ranging from 200 Hz to 200 kHz, and DC) measurements were taken at various temperatures ranging from 30 to 60 °C by the parallel plate capacitor method. The electrical parameters considered are found to increase with the increase in temperature. The AC and DC activation energies were also estimated. The observed high dielectric constants and good second harmonic generation efficiency indicate that the crystal is expected to be useful in capacitor technology and photonic devices.

  7. Spectrophotometric titration of bimetallic metal cation binding in polyamido(amine) dendrimer templates.

    PubMed

    Marvin, Katherine A; Johnson, Justin A; Rodenbusch, Stacia E; Gong, Lucy; Vanden Bout, David A; Stevenson, Keith J

    2012-06-05

    Spectrophotometric titration and a binding isotherm were used to accurately assess the loading capacity of generation four polyamido(amine) (PAMAM) dendrimer templates with terminal alcohol groups (G4-OH). Preparation of bimetallic G4-OH dendrimer-encapsulated metal nanoclusters (DENs) necessitates knowledge of the precise metal-ion binding capacity. The binding of metal ions such as Pt(2+) and Pd(2+) has proven difficult to assess via UV-vis spectroscopy because the absorbance shifts associated with metal-ion binding within the dendrimer template are masked by the absorbance of the PAMAM dendrimer itself. In contrast, the binding of Cu(2+) to G4-OH PAMAM dendrimer results in a strong, distinct absorption band at 300 nm, making UV-vis spectrophotometric titration with copper straightforward. Here we use copper binding as a means to assess the number of binding sites remaining within the PAMAM G4-OH dendrimer after the complexation of a specified molar excess of Pd(2+) or Pt(2+). In addition, we use a binding isotherm to mathematically estimate the loading capacity of the dendrimer in each case. The loading capacities for M(2+) in the G4-OH dendrimer were found to be ∼16 for copper alone, ∼21 for copper combined with palladium, and ∼25 for copper combined with platinum.

  8. Selective hydrogen production from formic acid decomposition on Pd-Au bimetallic surfaces.

    PubMed

    Yu, Wen-Yueh; Mullen, Gregory M; Flaherty, David W; Mullins, C Buddie

    2014-08-06

    Pd-Au catalysts have shown exceptional performance for selective hydrogen production via HCOOH decomposition, a promising alternative to solve issues associated with hydrogen storage and distribution. In this study, we utilized temperature-programmed desorption (TPD) and reactive molecular beam scattering (RMBS) in an attempt to unravel the factors governing the catalytic properties of Pd-Au bimetallic surfaces for HCOOH decomposition. Our results show that Pd atoms at the Pd-Au surface are responsible for activating HCOOH molecules; however, the selectivity of the reaction is dictated by the identity of the surface metal atoms adjacent to the Pd atoms. Pd atoms that reside at Pd-Au interface sites tend to favor dehydrogenation of HCOOH, whereas Pd atoms in Pd(111)-like sites, which lack neighboring Au atoms, favor dehydration of HCOOH. These observations suggest that the reactivity and selectivity of HCOOH decomposition on Pd-Au catalysts can be tailored by controlling the arrangement of surface Pd and Au atoms. The findings in this study may prove informative for rational design of Pd-Au catalysts for associated reactions including selective HCOOH decomposition for hydrogen production and electro-oxidation of HCOOH in the direct formic acid fuel cell.

  9. Chemical Sensors Based on Metal Oxide Nanostructures

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

  10. Composite materials formed with anchored nanostructures

    DOEpatents

    Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

    2015-03-10

    A method of forming nano-structure composite materials that have a binder material and a nanostructure fiber material is described. A precursor material may be formed using a mixture of at least one metal powder and anchored nanostructure materials. The metal powder mixture may be (a) Ni powder and (b) NiAl powder. The anchored nanostructure materials may comprise (i) NiAl powder as a support material and (ii) carbon nanotubes attached to nanoparticles adjacent to a surface of the support material. The process of forming nano-structure composite materials typically involves sintering the mixture under vacuum in a die. When Ni and NiAl are used in the metal powder mixture Ni.sub.3Al may form as the binder material after sintering. The mixture is sintered until it consolidates to form the nano-structure composite material.

  11. Reduced oxide sites and surface corrugation affecting the reactivity, thermal stability, and selectivity of supported Au-Pd bimetallic clusters on SiO2/Si(100).

    PubMed

    Gross, Elad; Sorek, Elishama; Murugadoss, Arumugam; Asscher, Micha

    2013-05-21

    The morphology and surface elemental composition of Au-Pd bimetallic nanoclusters are reported to be sensitive to and affected by reduced silicon defect sites and structural corrugation on SiO2/Si(100), generated by argon ion sputtering under ultrahigh vacuum (UHV) conditions. Metastable structures of the bimetallic clusters, where Au atoms are depleted from the top surface upon annealing, are stabilized by the interaction with the reduced silica sites, as indicated from CO temperature programmed desorption (TPD) titration measurements. Acetylene conversion to ethylene and benzene has been studied as a probe reaction, revealing the modification of selectivity and reactivity enhancement in addition to improved thermal stability on substrates rich in reduced-silica sites. These observations suggest that these unique sites play an important role in anchoring thermodynamically metastable conformations of supported Au-Pd bimetallic catalysts and dictate their high-temperature activity.

  12. Ag/Au bi-metallic film based color surface plasmon resonance biosensor with enhanced sensitivity, color contrast and great linearity.

    PubMed

    Li, Chung-Tien; Lo, Kun-Chi; Chang, Hsin-Yun; Wu, Hsieh-Ting; Ho, Jennifer H; Yen, Ta-Jen

    2012-01-01

    In wavelength surface plasmon resonance (SPR) biosensor, the manipulation of SPR dispersion relation by Ag/Au bi-metallic film was first time implemented. Due to the enhanced resonant wavelength shift and the sharper SPR slope of using Ag/Au bi-metallic film, the illuminated color of reflection shows one order of magnitude greater contrast than conventional SPR biosensors. Such an Ag/Au bi-metallic film based color SPR biosensor (CSPRB) allows the detail bio-interactions, for example 100 nM streptavidin, to be distinguished by directly observing the color change of reflection through naked eyes rather than the analysis of spectrometer. In addition to the enhanced sensitivity and color contrast, this CSPRB also possesses a great linear detection range up to 0.0254 RIU, which leading to the application of point-of-care tests.

  13. Raman Studies of Carbon Nanostructures

    NASA Astrophysics Data System (ADS)

    Jorio, Ado; Souza Filho, Antonio G.

    2016-07-01

    This article reviews recent advances on the use of Raman spectroscopy to study and characterize carbon nanostructures. It starts with a brief survey of Raman spectroscopy of graphene and carbon nanotubes, followed by recent developments in the field. Various novel topics, including Stokes-anti-Stokes correlation, tip-enhanced Raman spectroscopy in two dimensions, phonon coherence, and high-pressure and shielding effects, are presented. Some consequences for other fields—quantum optics, near-field electromagnetism, archeology, materials and soil sciences—are discussed. The review ends with a discussion of new perspectives on Raman spectroscopy of carbon nanostructures, including how this technique can contribute to the development of biotechnological applications and nanotoxicology.

  14. Nanorice: a new hybrid nanostructure

    NASA Astrophysics Data System (ADS)

    Nordlander, P.; Brandl, D.; Le, F.; Wang, H.; Halas, N. J.

    2006-03-01

    The plasmon hybridization method [1] is applied to nanorice, a new metallic nanostructure which combines the properties of two popular tunable plasmonic nanoparticle geometries: nanorods and nanoshells. The particle consists of a prolate spheroidal dielectric core and a thin metallic shell, bearing a remarkable resemblance to a rice grain. The nanorice particle shows far greater geometric tunability of the optical resonance, larger local field intensity enhancements and far greater sensitivity as a surface plasmon resonance (SPR) nanosensor than any previously reported dielectric-metal nanostructure. The tunability of the nanorice particle arises from the interaction of primitive plasmons associated with the inner and outer surfaces of the shell. The results from plasmon hybridization are compared to FDTD simulations. [1] E. Prodan and P. Nordlander, J. Chem. Phys. 120(2004)5444-5454

  15. Nanostructured materials for thermoelectric applications.

    PubMed

    Bux, Sabah K; Fleurial, Jean-Pierre; Kaner, Richard B

    2010-11-28

    Recent studies indicate that nanostructuring can be an effective method for increasing the dimensionless thermoelectric figure of merit (ZT) in materials. Most of the enhancement in ZT can be attributed to large reductions in the lattice thermal conductivity due to increased phonon scattering at interfaces. Although significant gains have been reported, much higher ZTs in practical, cost-effective and environmentally benign materials are needed in order for thermoelectrics to become effective for large-scale, wide-spread power and thermal management applications. This review discusses the various synthetic techniques that can be used in the production of bulk scale nanostructured materials. The advantages and disadvantages of each synthetic method are evaluated along with guidelines and goals presented for an ideal thermoelectric material. With proper optimization, some of these techniques hold promise for producing high efficiency devices.

  16. Nanostructured Biomaterials and Their Applications

    PubMed Central

    Parratt, Kirsten; Yao, Nan

    2013-01-01

    Some of the most important advances in the life sciences have come from transitioning to thinking of materials and their properties on the nanoscale rather than the macro or even microscale. Improvements in imaging technology have allowed us to see nanofeatures that directly impact chemical and mechanical properties of natural and man-made materials. Now that these can be imaged and quantified, substantial advances have been made in the fields of biomimetics, tissue engineering, and drug delivery. For the first time, scientists can determine the importance of nanograins and nanoasperities in nacre, direct the nucleation of apatite and the growth of cells on nanostructured scaffolds, and pass drugs tethered to nanoparticles through the blood-brain barrier. This review examines some of the most interesting materials whose nanostructure and hierarchical organization have been shown to correlate directly with favorable properties and their resulting applications.

  17. Dispersive interactions in graphitic nanostructures

    NASA Astrophysics Data System (ADS)

    Woods, L. M.; Popescu, A.; Drosdoff, D.; Bondarev, I. V.

    2013-02-01

    The Casimir interaction between graphitic nanostructures, such as carbon nanotubes and graphene sheets, is investigated at the quantum mechanical limit (T = 0 K) using a quantum electrodynamical approach for absorbing and dispersive media. It is found that the nanotube/nanotube interaction in a double wall carbon nanotube configuration is profoundly affected by the collective low frequency excitations of individual nanotubes. It is shown that pronounced, low frequency peaks in the nanotube electron energy loss spectra are a main factor contributing to the strength of the intertube attraction. The graphene/graphene force is also investigated. It is obtained that the graphene optical transparency is the main reason for the reduced attraction as compared to the one for perfect metals. This study presents a unified approach for electromagnetic interactions in graphitic nanostructures, which is able to account for their unique electronic and response properties and geometry configurations.

  18. Advanced electron microscopy characterization of multimetallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Khanal, Subarna Raj

    Research in noble metal nanoparticles has led to exciting progress in a versatile array of applications. For the purpose of better tailoring of nanoparticles activities and understanding the correlation between their structures and properties, control over the composition, shape, size and architecture of bimetallic and multimetallic nanomaterials plays an important role on revealing their new or enhanced functions for potentials application. Advance electron microscopy techniques were used to provide atomic scale insights into the structure-properties of different materials: PtPd, Au-Au3Cu, Cu-Pt, AgPd/Pt and AuCu/Pt nanoparticles. The objective of this work is to understand the physical and chemical properties of nanomaterials and describe synthesis, characterization, surface properties and growth mechanism of various bimetallic and multimetallic nanoparticles. The findings have provided us with novel and significant insights into the physical and chemical properties of noble metal nanoparticles. Different synthesis routes allowed us to synthesize bimetallic: Pt-Pd, Au-Au3Cu, Cu-Pt and trimetallic: AgPd/Pt, AuCu/Pt, core-shell and alloyed nanoparticles with monodispersed sizes, controlled shapes and tunable surface properties. For example, we have synthesized the polyhedral PtPd core-shell nanoparticles with octahedral, decahedral, and triangular plates. Decahedral PtPd core-shell structures are novel morphologies for this system. For the first time we fabricated that the Au core and Au3Cu alloyed shell nanoparticles passivated with CuS2 surface layers and characterized by Cs-corrected scanning transmission electron microscopy. The analysis of the high-resolution micrographs reveals that these nanoparticles have decahedral structure with shell periodicity, and that each of the particles is composed by Au core and Au3Cu ordered superlattice alloyed shell surrounded by CuS 2 surface layer. Additionally, we have described both experimental and theoretical methods of

  19. Thermoelectric effects in graphene nanostructures

    NASA Astrophysics Data System (ADS)

    Dollfus, Philippe; Nguyen, Viet Hung; Saint-Martin, Jérôme

    2015-04-01

    The thermoelectric properties of graphene and graphene nanostructures have recently attracted significant attention from the physics and engineering communities. In fundamental physics, the analysis of Seebeck and Nernst effects is very useful in elucidating some details of the electronic band structure of graphene that cannot be probed by conductance measurements alone, due in particular to the ambipolar nature of this gapless material. For applications in thermoelectric energy conversion, graphene has two major disadvantages. It is gapless, which leads to a small Seebeck coefficient due to the opposite contributions of electrons and holes, and it is an excellent thermal conductor. The thermoelectric figure of merit ZT of a two-dimensional (2D) graphene sheet is thus very limited. However, many works have demonstrated recently that appropriate nanostructuring and bandgap engineering of graphene can concomitantly strongly reduce the lattice thermal conductance and enhance the Seebeck coefficient without dramatically degrading the electronic conductance. Hence, in various graphene nanostructures, ZT has been predicted to be high enough to make them attractive for energy conversion. In this article, we review the main results obtained experimentally and theoretically on the thermoelectric properties of graphene and its nanostructures, emphasizing the physical effects that govern these properties. Beyond pure graphene structures, we discuss also the thermoelectric properties of some hybrid graphene structures, as graphane, layered carbon allotropes such as graphynes and graphdiynes, and graphene/hexagonal boron nitride heterostructures which offer new opportunities. Finally, we briefly review the recent activities on other atomically thin 2D semiconductors with finite bandgap, i.e. dichalcogenides and phosphorene, which have attracted great attention for various kinds of applications, including thermoelectrics.

  20. Dielectric nanostructures with high laser damage threshold

    NASA Astrophysics Data System (ADS)

    Ngo, C. Y.; Hong, L. Y.; Deng, J.; Khoo, E. H.; Liu, Z.; Wu, R. F.; Teng, J. H.

    2017-02-01

    Dielectric-based metamaterials are proposed to be the ideal candidates for low-loss, high-efficiency devices. However, to employ dielectric nanostructures for high-power applications, the dielectric material must have a high laser-induced damaged threshold (LIDT) value. In this work, we investigated the LIDT values of dielectric nanostructures for high-power fiber laser applications. Consequently, we found that the fabricated SiO2 nanostructured lens can withstand laser fluence exceeding 100 J/cm2.

  1. Nanostructured conducting polymers and their biomedical applications.

    PubMed

    Wang, G W; Lu, Y N; Wang, L P; Wang, H J; Wang, J Y

    2014-01-01

    Much attention has been paid to nanostructured conducting polymers due to their unique properties, which arise from their nanoscale size, such as their large surface area, high electrical conductivity, electrochemical stability and quantum effects. This article reviews three methods to synthesize nanostructured conducting polymers and their applications in the biomedical field, focusing specifically on neural probes, biosensors, artificial muscles or actuators and controlled drug release. Challenges and future directions of these nanostructured conducting polymer are also discussed.

  2. Sintering and ripening resistant noble metal nanostructures

    DOEpatents

    van Swol, Frank B; Song, Yujiang; Shelnutt, John A; Miller, James E; Challa, Sivakumar R

    2013-09-24

    Durable porous metal nanostructures comprising thin metal nanosheets that are metastable under some conditions that commonly produce rapid reduction in surface area due to sintering and/or Ostwald ripening. The invention further comprises the method for making such durable porous metal nanostructures. Durable, high-surface area nanostructures result from the formation of persistent durable holes or pores in metal nanosheets formed from dendritic nanosheets.

  3. Optical properties of chiral nanostructures

    NASA Astrophysics Data System (ADS)

    Cecilia, Noguez; Román-Velázquez, Carlos E.; Garzón, Ignacio L.

    2004-03-01

    We present a computational model to study the optical properties chiral nanostructures[1] . In this work the nanostructures of interest are composed by N atoms, where each one is represented by a polarizable point dipole located at theposition of the atom. We assume that the dipole located is characterized by a polarizability. The nanostructure is excited by a circularly polarized incident wave, such that, each dipole is subject to a total electric field due to: (i) the incident radiation field, plus (ii) the radiation field resulting from all of the other induced dipoles. Once we solve the complex-linear equations, the dipole moment on each atom in the cluster can be determined and we can find the extinction cross section of the whole nanoparticle. Circular dichroism (CD) spectra of chiral bare and thiol-passivated gold nanoclusters have been calculated within the dipole approximation. The calculated CD spectra show features that allow us to distinguish between clusters with different indexes of chirality. The main factor responsible of the differences in the CD lineshapes is the distribution of interatomic distances that characterize the chiral cluster geometry. These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral metal nanoclusters. [1] C. E. Roman-Velazquez, et al., J. of Phys. Chem. B (Letter) 107, 12035 (2003) This work has been partly supported by DGAPA-UNAM grants No. IN104201 and IN104402, and by CONACyT grant 36651-E.

  4. Photoinduced magnetic force between nanostructures

    NASA Astrophysics Data System (ADS)

    Guclu, Caner; Tamma, Venkata Ananth; Wickramasinghe, Hemantha Kumar; Capolino, Filippo

    2015-12-01

    Photoinduced magnetic force between nanostructures, at optical frequencies, is investigated theoretically. Till now optical magnetic effects were not used in scanning probe microscopy because of the vanishing natural magnetism with increasing frequency. On the other hand, artificial magnetism in engineered nanostructures led to the development of measurable optical magnetism. Here two examples of nanoprobes that are able to generate strong magnetic dipolar fields at optical frequency are investigated: first, an ideal magnetically polarizable nanosphere and then a circular cluster of silver nanospheres that has a looplike collective plasmonic resonance equivalent to a magnetic dipole. Magnetic forces are evaluated based on nanostructure polarizabilities, i.e., induced magnetic dipoles, and magnetic-near field evaluations. As an initial assessment on the possibility of a magnetic nanoprobe to detect magnetic forces, we consider two identical magnetically polarizable nanoprobes and observe magnetic forces on the order of piconewtons, thereby bringing it within detection limits of conventional atomic force microscopes at ambient pressure and temperature. The detection of magnetic force is a promising method in studying optical magnetic transitions that can be the basis of innovative spectroscopy applications.

  5. Physical electrochemistry of nanostructured devices.

    PubMed

    Bisquert, Juan

    2008-01-07

    This Perspective reviews recent developments in experimental techniques and conceptual methods applied to the electrochemical properties of metal-oxide semiconductor nanostructures and organic conductors, such as those used in dye-sensitized solar cells, high-energy batteries, sensors, and electrochromic devices. The aim is to provide a broad view of the interpretation of electrochemical and optoelectrical measurements for semiconductor nanostructures (sintered colloidal particles, nanorods, arrays of quantum dots, etc.) deposited or grown on a conducting substrate. The Fermi level displacement by potentiostatic control causes a broad change of physical properties such as the hopping conductivity, that can be investigated over a very large variation of electron density. In contrast to traditional electrochemistry, we emphasize that in nanostructured devices we must deal with systems that depart heavily from the ideal, Maxwell-Boltzmann statistics, due to broad distributions of states (energy disorder) and interactions of charge carriers, therefore the electrochemical analysis must be aided by thermodynamics and statistical mechanics. We discuss in detail the most characteristic densities of states, the chemical capacitance, and the transport properties, specially the chemical diffusion coefficient, mobility, and generalized Einstein relation.

  6. Precise replication of antireflective nanostructures from biotemplates

    NASA Astrophysics Data System (ADS)

    Gao, Hongjun; Liu, Zhongfan; Zhang, Jin; Zhang, Guoming; Xie, Guoyong

    2007-03-01

    The authors report herein a new type of nanonipple structures on the cicada's eye and the direct structural replication of the complex micro- and nanostructures for potential functional emulation. A two-step direct molding process is developed to replicate these natural micro- and nanostructures using epoxy resin with high fidelity, which demonstrates a general way of fabricating functional nanostructures by direct replication of natural biotemplates via a suitable physicochemical process. Measurements of spectral reflectance showed that this kind of replicated nanostructure has remarkable antireflective property, suggestive of its potential applications to optical devices.

  7. Particle Lithography Enables Fabrication of Multicomponent Nanostructures

    PubMed Central

    Lin, Wei-feng; Swartz, Logan A.; Li, Jie-Ren; Liu, Yang; Liu, Gang-yu

    2014-01-01

    Multicomponent nanostructures with individual geometries have attracted much attention because of their potential to carry out multiple functions synergistically. The current work reports a simple method using particle lithography to fabricate multicomponent nanostructures of metals, proteins, and organosiloxane molecules, each with its own geometry. Particle lithography is well-known for its capability to produce arrays of triangular-shaped nanostructures with novel optical properties. This paper extends the capability of particle lithography by combining a particle template in conjunction with surface chemistry to produce multicomponent nanostructures. The advantages and limitations of this approach will also be addressed. PMID:24707328

  8. Processing Nanostructured Sensors Using Microfabrication Techniques

    NASA Technical Reports Server (NTRS)

    Hunter, Gary W.; VanderWal, Randall L.; Evans, Laura J.; Xu, Jennifer C.

    2010-01-01

    Standard microfabrication techniques can be implemented and scaled to help assemble nanoscale microsensors. Currently nanostructures are often deposited onto materials primarily by adding them to a solution, then applying the solution in a thin film. This results in random placement of the nanostructures with no controlled order, and no way to accurately reproduce the placement. This method changes the means by which microsensors with nanostructures are fabricated. The fundamental advantage to this approach is that it enables standard microfabrication techniques to be applied in the repeated manufacture of nanostructured sensors on a microplatform.

  9. Is there a shift to "active nanostructures"?

    NASA Astrophysics Data System (ADS)

    Subramanian, Vrishali; Youtie, Jan; Porter, Alan L.; Shapira, Philip

    2010-01-01

    It has been suggested that an important transition in the long-run trajectory of nanotechnology development is a shift from passive to active nanostructures. Such a shift could present different or increased societal impacts and require new approaches for risk assessment. An active nanostructure "changes or evolves its state during its operation," according to the National Science Foundation's (2006) Active Nanostructures and Nanosystems grant solicitation. Active nanostructure examples include nanoelectromechanical systems (NEMS), nanomachines, self-healing materials, targeted drugs and chemicals, energy storage devices, and sensors. This article considers two questions: (a) Is there a "shift" to active nanostructures? (b) How can we characterize the prototypical areas into which active nanostructures may emerge? We build upon the NSF definition of active nanostructures to develop a research publication search strategy, with a particular intent to distinguish between passive and active nanotechnologies. We perform bibliometric analyses and describe the main publication trends from 1995 to 2008. We then describe the prototypes of research that emerge based on reading the abstracts and review papers encountered in our search. Preliminary results suggest that there is a sharp rise in active nanostructures publications in 2006, and this rise is maintained in 2007 and through to early 2008. We present a typology that can be used to describe the kind of active nanostructures that may be commercialized and regulated in the future.

  10. Anchored nanostructure materials and method of fabrication

    DOEpatents

    Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

    2012-11-27

    Anchored nanostructure materials and methods for their fabrication are described. The anchored nanostructure materials may utilize nano-catalysts that include powder-based or solid-based support materials. The support material may comprise metal, such as NiAl, ceramic, a cermet, or silicon or other metalloid. Typically, nanoparticles are disposed adjacent a surface of the support material. Nanostructures may be formed as anchored to nanoparticles that are adjacent the surface of the support material by heating the nano-catalysts and then exposing the nano-catalysts to an organic vapor. The nanostructures are typically single wall or multi-wall carbon nanotubes.

  11. Synthesis of Silver Nanostructures by Multistep Methods

    PubMed Central

    Zhang, Tong; Song, Yuan-Jun; Zhang, Xiao-Yang; Wu, Jing-Yuan

    2014-01-01

    The shape of plasmonic nanostructures such as silver and gold is vital to their physical and chemical properties and potential applications. Recently, preparation of complex nanostructures with rich function by chemical multistep methods is the hotspot of research. In this review we introduce three typical multistep methods to prepare silver nanostructures with well-controlled shapes, including the double reductant method, etching technique and construction of core-shell nanostructures. The growth mechanism of double the reductant method is that different favorable facets of silver nanocrystals are produced in different reductants, which can be used to prepare complex nanostructures such as nanoflags with ultranarrow resonant band bandwidth or some silver nanostructures which are difficult to prepare using other methods. The etching technique can selectively remove nanoparticles to achieve the aim of shape control and is widely used for the synthesis of nanoflowers and hollow nanostructures. Construction of core-shell nanostructures is another tool to control shape and size. The three methods can not only prepare various silver nanostructures with well-controlled shapes, which exhibit unique optical properties, such as strong surface-enhanced Raman scattering (SERS) signal and localized surface plasmon resonance (LSPR) effect, but also have potential application in many areas. PMID:24670722

  12. Nanostructures having crystalline and amorphous phases

    DOEpatents

    Mao, Samuel S; Chen, Xiaobo

    2015-04-28

    The present invention includes a nanostructure, a method of making thereof, and a method of photocatalysis. In one embodiment, the nanostructure includes a crystalline phase and an amorphous phase in contact with the crystalline phase. Each of the crystalline and amorphous phases has at least one dimension on a nanometer scale. In another embodiment, the nanostructure includes a nanoparticle comprising a crystalline phase and an amorphous phase. The amorphous phase is in a selected amount. In another embodiment, the nanostructure includes crystalline titanium dioxide and amorphous titanium dioxide in contact with the crystalline titanium dioxide. Each of the crystalline and amorphous titanium dioxide has at least one dimension on a nanometer scale.

  13. Acetylene trimerization on Ag, Pd and Rh atoms deposited on MgO thin films.

    PubMed

    Judai, Ken; Wörz, Anke S; Abbet, Stéphane; Antonietti, Jean-Marie; Heiz, Ueli; Del Vitto, Annalisa; Giordano, Livia; Pacchioni, Gianfranco

    2005-03-07

    The acetylene trimerization on the group VIII transition metal atoms, Rh and Pd, as well as on Ag atoms supported on MgO thin films has been studied experimentally and theoretically. The three metal atoms with the atomic configurations 4d(8)5s1 (Rh), 4d10s0 (Pd) and 4d(10)5s1 (Ag) behave distinctly differently. The coinage metal atom silver is basically inert for this reaction, whereas Pd is active at 220 and 320 K, and Rh produces benzene in a rather broad temperature range from 350 to ca. 430 K. The origins of these differences are not only the different electronic configurations, leading to a weak interaction of acetylene with silver due to strong Pauli repulsion with the 5s electron but also the different stability and dynamics of the three atoms on the MgO surface. In particular, Rh and Pd atoms interact differently with surface defects like the oxygen vacancies (F centers) and the step edges. Pd atoms migrate already at low temperature exclusively to F centers where the cyclotrimerization is efficiently promoted. The Rh atoms on the other hand are not only trapped on F centers but also at step edges up to about 300 K. Interestingly, only Rh atoms on F centers catalyze the trimerization reaction whereas they are turned inert on the step edges due to strong steric effects.

  14. Bottom-up multiferroic nanostructures

    NASA Astrophysics Data System (ADS)

    Ren, Shenqiang

    Multiferroic and especially magnetoelectric (ME) nanocomposites have received extensive attention due to their potential applications in spintronics, information storage and logic devices. The extrinsic ME coupling in composites is strain mediated via the interface between the piezoelectric and magnetostrictive components. However, the design and synthesis of controlled nanostructures with engineering enhanced coupling remain a significant challenge. The purpose of this thesis is to create nanostructures with very large interface densities and unique connectivities of the two phases in a controlled manner. Using inorganic solid state phase transformations and organic block copolymer self assembly methodologies, we present novel self assembly "bottom-up" techniques as a general protocol for the nanofabrication of multifunctional devices. First, Lead-Zirconium-Titanate/Nickel-Ferrite (PZT/NFO) vertical multilamellar nanostructures have been produced by crystallizing and decomposing a gel in a magnetic field below the Curie temperature of NFO. The ensuing microstructure is nanoscopically periodic and anisotropic. The wavelength of the PZT/NFO alternation, 25 nm, agrees within a factor of two with the theoretically estimated value. The macroscopic ferromagnetic and magnetoelectric responses correspond qualitatively and semi-quantitatively to the features of the nanostructure. The maximum of the field dependent magnetoelectric susceptibility equals 1.8 V/cm Oe. Second, a magnetoelectric composite with controlled nanostructures is synthesized using co-assembly of two inorganic precursors with a block copolymer. This solution processed material consists of hexagonally arranged ferromagnetic cobalt ferrite (CFO) nano-cylinders within a matrix of ferroelectric Lead-Zirconium-Titanate (PZT). The initial magnetic permeability of the self-assembled CFO/PZT nanocomposite changes by a factor of 5 through the application of 2.5 V. This work may have significant impact on the

  15. Material property evaluations of bimetallic welds, stainless steel saw fusion lines, and materials affected by dynamic strain aging

    SciTech Connect

    Rudland, D.; Scott, P.; Marschall, C.; Wilkowski, G.

    1997-04-01

    Pipe fracture analyses can often reasonably predict the behavior of flawed piping. However, there are material applications with uncertainties in fracture behavior. This paper summarizes work on three such cases. First, the fracture behavior of bimetallic welds are discussed. The purpose of the study was to determine if current fracture analyses can predict the response of pipe with flaws in bimetallic welds. The weld joined sections of A516 Grade 70 carbon steel to F316 stainless steel. The crack was along the carbon steel base metal to Inconel 182 weld metal fusion line. Material properties from tensile and C(T) specimens were used to predict large pipe response. The major conclusion from the work is that fracture behavior of the weld could be evaluated with reasonable accuracy using properties of the carbon steel pipe and conventional J-estimation analyses. However, results may not be generally true for all bimetallic welds. Second, the toughness of austenitic steel submerged-arc weld (SAW) fusion lines is discussed. During large-scale pipe tests with flaws in the center of the SAW, the crack tended to grow into the fusion line. The fracture toughness of the base metal, the SAW, and the fusion line were determined and compared. The major conclusion reached is that although the fusion line had a higher initiation toughness than the weld metal, the fusion-line J-R curve reached a steady-state value while the SAW J-R curve increased. Last, carbon steel fracture experiments containing circumferential flaws with periods of unstable crack jumps during steady ductile tearing are discussed. These instabilities are believed to be due to dynamic strain aging (DSA). The paper discusses DSA, a screening criteria developed to predict DSA, and the ability of the current J-based methodologies to assess the effect of these crack instabilities. The effect of loading rate on the strength and toughness of several different carbon steel pipes at LWR temperatures is also discussed.

  16. Role of the metal in the bonding and properties of bimetallic complexes involving manganese, iron, and cobalt.

    PubMed

    Tereniak, Stephen J; Carlson, Rebecca K; Clouston, Laura J; Young, Victor G; Bill, Eckhard; Maurice, Rémi; Chen, Yu-Sheng; Kim, Hyun Jung; Gagliardi, Laura; Lu, Connie C

    2014-02-05

    A multidentate ligand platform is introduced that enables the isolation of both homo- and heterobimetallic complexes of divalent first-row transition metal ions such as Mn(II), Fe(II), and Co(II). By means of a two-step metalation strategy, five bimetallic coordination complexes were synthesized with the general formula M1M2Cl(py3tren), where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. The metal-metal pairings include dicobalt (1), cobalt-iron (2), cobalt-manganese (3), diiron (4), and iron-manganese (5). The bimetallic complexes have been investigated by X-ray diffraction and X-ray anomalous scattering studies, cyclic voltammetry, magnetometry, Mössbauer spectroscopy, UV-vis-NIR spectroscopy, NMR spectroscopy, combustion analyses, inductively coupled plasma optical emission spectrometry, and ab initio quantum chemical methods. Only the diiron chloride complex in this series contains a metal-metal single bond (2.29 Å). The others show weak metal-metal interactions (2.49 to 2.53 Å). The diiron complex is also distinct with a septet ground state, while the other bimetallic species have much lower spin states from S = 0 to S = 1. We propose that the diiron system has delocalized metal-metal bonding electrons, which seems to correlate with a short metal-metal bond and a higher spin state. Multiconfigurational wave function calculations revealed that, indeed, the metal-metal bonding orbitals in the diiron complex are much more delocalized than those of the dicobalt analogue.

  17. Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

    SciTech Connect

    Zhang, Haijun; Deng, Xiangong; Jiao, Chengpeng; Lu, Lilin; Zhang, Shaowei

    2016-07-15

    Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.

  18. Mono- and bimetallic manganese-carbonyl complexes and clusters bearing imidazol(in)ium-2-dithiocarboxylate ligands.

    PubMed

    Beltrán, Tomás F; Zaragoza, Guillermo; Delaude, Lionel

    2017-02-14

    Five complexes with the generic formula fac-[MnBr(CO)3(S2C·NHC)] were obtained by reacting [MnBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The mononuclear Mn(i) derivatives were coupled with Na[Mn(CO)5] to afford bimetallic [Mn2(CO)6(S2C·NHC)] clusters. Yet, the most convenient strategy to access these dinuclear Mn(0) products implied a direct carbonyl substitution from the [Mn2(CO)10] dimer. The molecular structures of three monometallic and four bimetallic compounds were elucidated by single crystal X-ray diffraction analysis. In the monometallic complexes, the NHC·CS2 ligands exhibited a bidentate κ(2)-S,S' coordination mode with an S-C-S bite angle of about 116°. In the dinuclear clusters, the CS2(-) unit acted as a chelate toward one manganese center and as a pseudoallylic ligand toward the other one. The S-C-S bite angle was reduced to ca. 104°. Thus, the zwitterions displayed a remarkable flexibility, which also permitted a staggered arrangement of the carbonyl groups in the bimetallic systems. Examination of the [small nu, Greek, macron]CO absorption bands on IR spectroscopy helped identify the presence of fac-Mn(CO)3 or Mn2(CO)6 motifs, while the (13)C NMR chemical shift of the CS2(-) moiety was a reliable indicator for monitoring its hapticity. Whereas the dinuclear clusters were air- and moisture-stable crystalline solids, mononuclear halido derivatives displayed only a limited stability under aerobic conditions. Both types of compounds underwent rather unselective, extensive fragmentations in the gas phase, in sharp contrast with the analogous rhenium derivatives that led to clean sequential decarbonylation processes upon collision-induced dissociation.

  19. Synthesis of Pt-Pd bimetallic nanoparticles anchored on graphene for highly active methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Yuting; Chang, Gang; Shu, Honghui; Oyama, Munetaka; Liu, Xiong; He, Yunbin

    2014-09-01

    A simple, one-step reduction route was employed to synthesize bimetallic Pt-Pd nanoparticles (Pt-PdNPs) supported on graphene (G) sheets, in which the reduction of graphite oxide and metal precursor was carried out simultaneously using ascorbic acid as a soft reductant. The morphology and structure of Pt-PdNPs/G composites were characterized using X-ray diffraction, Transmission Electron Microscopy, Field Emission Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy analysis. The results show that Pt-Pd bimetallic nanoparticles were successfully synthesized and evenly anchored on the graphene sheets. Electrochemical experiments, including cyclic voltammetry and chronoamperometric measurements, were performed to investigate the electrochemical and electrocatalytic properties of the Pt-PdNPs/G composites. It was found that Pt-PdNPs/G composites show better electrocatalytic activity and stability towards the electro-oxidation of methanol than its counterparts such as composites composed of graphene-supported monometallic nanoparticles (PtNPs/G, PdNPs/G) and free-standing (Pt-PdNPs) and Vulcan-supported bimetallic Pt-Pd nanoparticles (Pt-PdNPs/V). The results could be attributed to the synergetic effects of the Pt-Pd nanoparticles and the enhanced electron transfer of graphene. The electrocatalytic activity of Pt-PdNPs/G changed with the Pd content in the Pt-Pd alloy, and the best performance was achieved with a Pt-Pd ratio of 1/3 in an alkaline environment. Our study indicates the potential use of Pt-PdNPs/G as new anode catalyst materials for direct methanol fuel cells.

  20. Modeling energy transport in nanostructures

    NASA Astrophysics Data System (ADS)

    Pattamatta, Arvind

    Heat transfer in nanostructures differ significantly from that in the bulk materials since the characteristic length scales associated with heat carriers, i.e., the mean free path and the wavelength, are comparable to the characteristic length of the nanostructures. Nanostructure materials hold the promise of novel phenomena, properties, and functions in the areas of thermal management and energy conversion. Example of thermal management in micro/nano electronic devices is the use of efficient nanostructured materials to alleviate 'hot spots' in integrated circuits. Examples in the manipulation of heat flow and energy conversion include nanostructures for thermoelectric energy conversion, thermophotovoltaic power generation, and data storage. One of the major challenges in Metal-Oxide Field Effect Transistor (MOSFET) devices is to study the 'hot spot' generation by accurately modeling the carrier-optical phonon-acoustic phonon interactions. Prediction of hotspot temperature and position in MOSFET devices is necessary for improving thermal design and reliability of micro/nano electronic devices. Thermoelectric properties are among the properties that may drastically change at nanoscale. The efficiency of thermoelectric energy conversion in a material is measured by a non-dimensional figure of merit (ZT) defined as, ZT = sigmaS2T/k where sigma is the electrical conductivity, S is the Seebeck coefficient, T is the temperature, and k is the thermal conductivity. During the last decade, advances have been made in increasing ZT using nanostructures. Three important topics are studied with respect to energy transport in nanostructure materials for micro/nano electronic and thermoelectric applications; (1) the role of nanocomposites in improving the thermal efficiency of thermoelectric devices, (2) the interfacial thermal resistance for the semiconductor/metal contacts in thermoelectric devices and for metallic interconnects in micro/nano electronic devices, (3) the